Journal of Hazardous Materials 422 (2022) 126778

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Journal of Hazardous Materials

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

Modification of coal fly ash and its use as low-cost adsorbent for the
removal of directive, acid and reactive dyes
Zawar Hussain a, Na Chang b, Jingqiu Sun c, Simeng Xiang b, Tehreem Ayaz d, Hao Zhang b,
Haitao Wang a, *
a
School of Material Science and Engineering, Tiangong University, No. 399 Binshui West Road, Xiqing District, Tianjin 300387, PR China
b
School of Textile Science and Engineering, Tiangong University, No. 399 Binshui West Road, Xiqing District, Tianjin 300387, PR China
c
State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 10085, PR China
d
College of Resources and Environment, Hunan Agricultural University, Changsha 410128, PR China

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

Editor: Dr. H. Artuto Directive, acid and reactive dyes are the carcinogenic dyes which have complex structures and difficult to remove
from the industrial wastewater. In this study, coal fly ash (CFA) was modified with HCl and NaOH solution and
Keywords: used for the removal of direct fast scarlet 4BS, direct sky blue 5B, acid navy blue R, and reactive turquoise blue
Adsorption capacity KN-G dyes. Laboratory experiments were carried out to analyze the performance of modified coal fly ash (MCFA)
Dye removal efficiency
to check the removal efficiency and adsorption capacity of dyes. The maximum removal efficiency of direct fast
Freundlich model
scarlet 4BS and direct sky blue 5B were recorded 96.03% and 93.820%, respectively using 0.05 g adsorbent
Langmuir model
Chemisorption dosage at 100 mg/L initial concentration. The results of MCFA were compared with carbon black, chitosan,
starch, zeolite and unmodified coal fly ash (UMCFA) at lower dosage 0.05 g and higher dosage 0.4 g. Adsorption
isotherm were analyzed by Langmuir and Freundlich model by different dyes concentrations, the result stated
that Freundlich and Langmuir model (±0.9918, ±0.9974) was fitted by chemisorption and physisorption
methods for all four dyes. Adsorption kinetic were also determined by Pseudo-first-order and Pseudo-second-
order at different contact times with dye molecules and adsorbent active sites, and the results showed that
the adsorption behaviors of all four dyes were described better by pseudo-second-order kinetics than pseudo-
first-order kinetics. Recommended dosage of modified fly ash is between 10 ‱ to 20 ‱ for simulated
textile industrial waste water and regeneration temperature is 300 ℃.

1. Introduction i.e. direct sky blue 5B, reactive turquoise blue KN-G, direct fast scarlet
4BS, and pigment scarlet R. These dyes are highly cytotoxic to humans
In last few years, dye wastewater has become a major challenge for and other mammalians, in addition they act as tumor enhancing sub­
clean water reservoirs due to its effects on water ecosystem. Dyes stops stances (Lin and Der Lee, 2016).
the sunlight transmission into fresh water, thus decreases photosyn­ Adsorption is a good technique for the removal of dyes and the
thesis and damages the food chain of water lives (Wang et al., 2018). treatment of industrial waste water, but this technique should be simple,
Dyes have complex aromatic structure, therefore, difficult to degrade environmentally friendly, adsorbable to the toxic pollutants, able to
and separate. Furthermore, dyes are highly toxic and carcinogenic (Liu treat all types of dye wastes, highly efficient, and economically signifi­
et al., 2019). There are many types of dyes which are used in textile cant (Astuti et al., 2019). There are many techniques which have been
industry, paper industry, food processing, dye manufacturing and tan­ studied and applied to remove dyes from wastewater such as physical,
nery industry (Yagub et al., 2014). Dyes can be categorized into cationic, chemical and biological methods (Zarrini et al., 2017). These techniques
anionic and non-ionic dyes. Among these, cationic dyes are more toxic have different criteria and processes to remove dyes include
than anionic and nonionic dyes, as cationic dyes cannot be degraded ion-exchange (Raghu and Basha, 2007), coagulation and flocculation
easily and can pass through the entire food chain (Rai et al., 2015). process (Yue et al., 2008; Man et al., 2012), membrane filtration process
There are some reactive and direct dyes which are mostly used in China, (Panda and De, 2015; Avlonitis et al., 2008), electrochemical and

* Corresponding author.
E-mail address: [email protected] (H. Wang).

https://doi.org/10.1016/j.jhazmat.2021.126778
Received 29 April 2021; Received in revised form 14 July 2021; Accepted 27 July 2021
Available online 3 August 2021
0304-3894/© 2021 Published by Elsevier B.V.
Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

electrolytic technology (Shen et al., 2006; He et al., 2010), biodegra­ 2.2. Modification of CFA
dation (Chang et al., 2001; Ali et al., 2009), sonochemical and sonoca­
talytic degradation (Moumeni and Hamdaoui, 2012; Khataee et al., Coal fly ash (30 g) was taken into a solution of 800 mL distilled
2015), photocatalytic degradation (Bojinova and Dushkin, 2011), solar water, and 40 mL HCl (5%). Acid solution having CFA was stirred for 2
degradation (Pirsaheb et al., 2016), UV-H2O2 degradation (Wei et al., hrs. at 30 ℃ in a water bath shaker machine (SHA-C) and then placed in
2012), and adsorption (Gong et al., 2009; Vuono et al., 2017). However, Ultrasonic cleaner machine (KH-250E) for 4 h at 40 ℃. Then the acid
such techniques have various limitations including, cost, efficiency, solution having CFA was mixed with 800 mL water, then the sample was
design and duration. Where, incrustation is the main problem of mem­ mixed with NaOH solution (140 g of NaOH in 860 mL of distilled water)
brane filtration (Sepehri and Sarrafzadeh, 2018), and it is difficult to until the CFA particles floated. The flocculent CFA particles’ color and
degrade dyes by light and oxidation reactions, because of complex dyes structure were also changed. The entire solution was turned into a basic
structure (Gong et al., 2013). Hence, the adsorption is the most appli­ solution and the pH 11 was maintained but the surface solution is
cable technique as it is economically efficient and preferable even at low neutral with a pH 7. The modified flocculant particles were separated
concentration of the adsorbent. without settled particles (Fig. 1) and filtered using Whatman filter paper
In the last few years urbanization and industrialization has been with the help of vacuum pump and neutralized with distilled water,
increased so that demand for energy is also increased. There are many maximum 8 g of flocculants particles from 30 g of CFA can be extracted.
sources of energy, but coal is the main natural source of energy which is Then the filtered MCFA was dried in electro-thermostatic blast oven
widely utilized for many decades. It fulfils about 25% energy requite­ (YLD-2000) for 8 h at 300 ℃. MCFA adsorbent was ready for
ment of the world (OECD. http: www.iea.org:stats:file:selstats:cotpese. application.
htm). Coal power plants play a vital role for the completion of global
demand of energy. Estimated 750 million tons of coal fly ash (CFA) is 2.3. Adsorption
annually generated, however only 25% of the generated CFA is used in
different fields (Hussain et al., 2020). There are many utilization fields Four kinds of reactive, acid and direct dyes i.e. direct fast scarlet 4BS,
for CFA as cement industry (Bhattacharjee and Kandpal, 2002), road direct sky blue 5B, acid navy blue R, and reactive turquoise blue were
construction, brick manicuring, landfill (Chaudhuri et al., 2015), selected for adsorption purpose. Different dosage of MCFA i.e., 0.05 g,
adsorption (Yuan et al., 2019), filer material with rubber (Hussain et al., 0.1 g 0.2 g, 0.3 g, 0.4 g, and 0.5 g and other regular adsorbents i.e.,
2020) and preparation of mesoporous silica and zeolite (Keleşoǧlu et al., carbon black, starch, zeolite, chitosan and unmodified CFA (UMCFA) at
2012; Sarkar and Banichul, 2013). a dosage of 0.05 g and 0.4 g were applied for the treatment of four kinds
Another uses of CFA is low-cost adsorbent for the removal of heavy of dye solutions (20 mL) with different concentrations i.e., 20 mg/L,
metal, organic and dyes from waste water (Zhang et al., 2016), due to its 40 mg/L, 60 mg/L, 80 mg/L, 100 mg/L, 120 mg/L, 140 mg/L, 160 mg/
availability, low cost and environmental consideration (Taufiq et al., L, 180 mg/L and 200 mg/L at 0.05 g MCFA adsorbent, and compared.
2018). Due to the low surface area and crystalline structure CFA waste Flasks having 20 mL of different dye concentration (20, 40, 60, 80, 100,
have usually low adsorption capacity. Therefore, the modification of 120, 140, 160, 180 and 200 mg/L each) solutions, with different dosages
CFA with chemical and physical methods have been investigated to of MCFA (0.05, 0.1, 0.2, 0.3, 0.4 and 0.5 g dosages each), at different pH
enhance the adsorption efficiency for dye contaminated wastewater. values (3, 5, 7, 9, 11) at 0.05 g adsorbent dosage and other regular ad­
Though, many researchers have modified CFA by various methods for sorbents (carbon black, starch, zeolite, chitosan and UMCFA) (0.05 and
the adsorption of different dyes. Treatment of CFA by different methods 0.4 g dosages each) were placed into water bath shaker machine for 2
increased its surface area and pore volume. CFA with 20 mL NaOH so­ hrs at 30 ℃ for possible removal efficiency and comparison. The
lution and heated the solution directly at 140 ℃ and then dried at 110 ℃ adsorption kinetics was also checked at different time intervals for lower
overnight (Wang et al., 2006). Gao et al. reported a simple method of dosage of adsorbent (0.05 g). MCFA adsorbent was also applied for the
CFA modification., Washed CFA was mixed with Na2FeO4 at 2:1 and removal of Chemical Oxygen Demand (COD) and sludge quantity of
heated at temperature 800 K for modification of CFA as dye adsorbent industrial wastewater. Regeneration of adsorbent (MCFA) was also
for methyl orange wastewater treatment (Gao et al., 2015). Banerjee checked at different temperatures i.e. 200 ℃, 300 ℃, 400 ℃, 500 ℃,
et al. applied HCl modified CFA for the discoloration of toxic dye 600 ℃ and 700 ℃. The best temperature of regeneration was selected
methylene blue, the CFA was mixed with HCl at 1:2 and the solution was for three times adsorption. The study was performed in triplicates and
then directly dried at 105 ℃ for 24 h (Banerjee et al., 2014). results represented the average value (S).
Although many studied have been conducted on the treatment of
dyes wastewater using CFA, but still more research is needed for the 2.4. Adsorption measurement
advanced and better information of the adsorption technique of dyes on
CFA. The study aims to modify maximum CFA and prepare maximum After 2 hrs. of adsorption process, the samples were filtered using
flocculant particles using HCl and NaOH solution to increase the surface Whatman filter paper and the wavelengths were analyzed using UV-
area of modified coal fly ash for the adsorption of four different dyes and Visible spectrophotometer (Evolution 201). The molecular weight,
make applicable for waste water treatment. structural formula and wavelength of the selected dyes are mentioned in
Table 1. Adsorption solution samples were checked before and after the
2. Materials and methods adsorption on the same wavelength as dyes mentioned using UV-Visible
spectrophotometer.
2.1. Materials Removal efficiency of all the samples in Abs were measured, and
calculated for the removal efficiency %, and adsorption capacity (Q)
Pulverized CFA was used from the leftover of our previous study using following equations (Zhang et al., 2020).
(Hussain et al., 2020). Hydrochloric acid (HCl), and sodium hydroxide
(C0 − C1) ∗ V
(NaOH) chemicals were purchased from Feng Chuan Chemical Reagent Q= (1)
m
Technology China. Other regular adsorbents like carbon black and
zeolite were acquired from Guangfu Fine Chemical Research Institute (C0 − C1)
Tianjin, China, Chitosan and starch were purchased from China National Removal efficiency% = ∗ 100 (2)
C0
Pharmaceutical Group Co. Ltd. Four kinds of dyes such as direct fast
scarlet 4BS, direct sky blue 5B, acid navy blue R, and reactive turquoise Were, C0: Concentration of the original dye),
blue KN-G were supplied from Tianjin Modern Chemical Plant China. C1: Concentration of the dye after adsorption,

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Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

Fig. 1. Flocculant’s and settled particles of morphological modified CFA in HCl and NaOH modification solution.

V: Volume of the dye (20 mL), the oxygen atoms in SiO2 and Al2O3 crystals. While, in MCFA, new O1s
m: Quantity of fly ash,Where C1 is calculated by following equation, peak merged at higher energy band near 536 eV and was attributed to
the oxygen atoms from polar groups such as carbonyl silicon hydroxyl,
C1 Abs1(after adsorption)
= (3) and carboxyl. The XPS analysis indicated that the number of OCG on
C0 Abs0(before adsorption)
MCFA has increased, and the structure of MCFA has changed after the
acid and base modification, so that it became a good adsorbent of dyes.
2.5. Sample analysis As these polar groups could enhance the hydrogen bonds and Van der
Waals’ forces among the dye molecules and adsorbent.
X-ray photoelectron spectroscopy (XPS) (Thermo ESCALAB 250XI) Fig. 2 shows that new elemental peaks appeared in the spectra of
was used for qualitative and semi quantitative analysis. The test area direct fast scarlet 4BS and Reactive Turquoise Blue (KN-G) loaded by
was generally sample information with a depth of 1–10 nm. The vacuum MCFA, corresponding to the S2p peak of sulfur atom at the binding
of the analysis chamber was 4 × 10–6 ~ 4 × 10–7 Pa, excitation source energy of 168 eV, and the N1s peak of nitrogen atom at the binding
was Al Kα ray (hv = 1486.6 eV), working voltage 14.6 kV, filament energy of 401 and 398 eV respectively, benzene sulfonic acid groups
current 13.5 mA, and the narrow scanning times were set according to (ph-SO3Na), phenylamino groups (ph-NH2) and azo groups are found in
the signal intensity, generally 2, 5 and 10. The passing energy was the dye conjugated system. The appearance of these elements is a strong
adjusted 20 eV, step size was 0.1 eV, and charge correction was carried proof that MCFA has adsorbed a considerable number of dye molecules.
out with the binding energy of C1s = 284.8 eV as the energy standard. In addition, from the element survey, the carbon content of dye loaded
Etching conditions (no etching, can be ignored): argon ion gun was used by MCFA was 47.02 ~ 47.06%, which was significantly higher than that
to etch the sample, the size of the etched spot was 1.5 mm, etching of MCFA and UMCFA (29.41 ~ 30.82%). At the same time, through the
voltage usually 2 kV, and etching rate was 0.05 nm/s (etching rate was analysis of C1 scan, it was found that there is a shoulder peak at the
only used as a reference). binding energy of 287 eV, which belongs to the methylene carbon (-
Fourier Infrared Spectrometer (Nicolet S50) was used to obtain CH2 -) in the benzene ring and carbon chain structure of the dye mo­
infrared (IR) spectrum for absorption. The surface morphology was lecular skeleton. This peak does not exist in the spectra of MCFA and
observed by Scanning electron microscopy (SEM) (Hitachi S-4800). All UMCFA. The result indicated that, there was not only carbon black but
samples were sprayed with gold to enhance the surface conductivity also a large amount of organic carbon on the surface of dye MCFA, which
before SEM measurements. was caused by a large amount of organic matter on its surface.

3. Results and discussion

3.2. SEM and BET analysis of UMCFA and MCFA
3.1. XPS analysis of UMCFA, MCFA and dye loaded MCFA
Scanning Electron Microscopy (SEM) was used to investigate the
Fig. 2 shows the XPS analysis of UMCFA, MCFA and dye loaded morphology of UMCFA, MCFA and loaded dyes samples. Fig. 3A shows
MCFA. The main components of UMCFA is Aluminosilicate (SiO2, Al2O3) the morphological changes of UMCFA. Flaky clusters and undefined
and small quantity of un-burned Carbon as mentioned in our previous irregular porous shapes were formed after acid and NaOH modification
study (Hussain et al., 2020). PHI 5000 Versaprobe: the true space of the (Fig. 3B). The smooth granular spherical surface of the UMCFA (Fig. 3A)
analysis chamber was 4xl0–6 ~ 4xl0–7 Pa, the excitation source was Al became irregular porous structures and various sized particles, thus
Kα ray (hv = 1486.6 eV), and the optical power was 0.05 nm/s 45 W. increased the adsorption of dyes. The modification of CFA increased the
The binding energy and other parameters are shown in the Fig. 2. The surface area of CFA, but after dyes adsorption the surface area has
number of narrow scans was adjusted according to the signal strength, i. decreased (Dash et al., 2016). The study found that the modification of
e., 2, 5 and 10. The charge correction was carried out with the binding CFA increased the pores and surface area of fly ash particles to increase
energy of C1s = 284.8 eV as per the energy standard. the adsorption.
In the C1s analysis (Fig. 2B) of UMCFA, the peak near binding energy Fig. 3C shows that, the particle structure and size of the MCFA
of 284 eV was assigned to carbon atoms of unburned coal. While, in adsorbent loaded by dye (4BS) did not change. However, the surface is
MCFA analysis new peak was emerged at 289 eV, that might be due to slightly rough, and organic matter like substances can be observed to
the acidic condition. A certain number of oxygen-containing groups stick to the particle surface, which was due to the accumulation of
(OCG) generated on the surface of carbon black, including C– – O, − OH, adsorbed dyes on the surface of MCFA. At the same time, it was found
COOH. From the analysis of O1s (Fig. 2C), same variation trend was that the tendency of adhesion and aggregation between particles in­
found. In UMCFA, the peak at binding energy of 531 eV was assigned to creases, which was due to the Van der Waals force and hydrogen bond

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Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

Table 1
Basic information of dyes before adsorption.

Molecular
M Wavelength
h
D
Dye Structural Formula
Weight
W (nm)

D
Direct

F
Fast

S
Scarlet

44BS 792.75
7 498.22

D
Direct

S
Sky Blue

55B 992.791
9 600.25

A
Acid

N
Navy

B
Blue R 695.58
6 624.36

R
Reactive

T
Turquoise

B
Blue

K
KN-G 1079.5494
1 661.10

force between dye molecules adsorbed on different particle surfaces, among the adsorbates.
resulting in the enhanced interaction between particles. The surface area of MCFA has increased from 4.501 m2/g to
Fig. 4 and Table 2, results of the Brunauer-Emmett-Teller (BET) 13.496 m2/g, which means that the MCFA has much more stronger
analysis using automated gas sorption analyzer (Autosorb-IQ-C BET) combining capacity and more potential binding sites to the adsorbates,
shows that the adsorption analysis of nitrogen molecules on the surfaces thus, the adsorption capacity of MCFA has been improved. The previous
of UMCFA and MCFA had a high fitting degree to the BET isotherm study stated that the surface area of modified fly ash by Na2FeO4
adsorption model, and the correlation coefficient (R) was greater than increased from 0.0784 m2/g to 1.4337 m2/g and 3.2784 m2/g (Gao
0.999, This also proves that the adsorption of adsorbate on the surface of et al., 2015), which is not higher for good adsorption.
modified fly ash is mainly physical adsorption and physical absorption,
and the adsorption is not monolayer, but multi-layer adsorption. In this
adsorption process, there is not only Van der Waals force between 3.3. X-ray powder diffraction (XRD) analysis of UMCFA and MCFA
adsorbent and adsorbate, but also Van der Waals force between adsor­
bate molecules, If the adsorbate molecules collide with the adsorbed X-ray Powder Diffraction (XRD) measurements were used to inves­
molecules, they may also be adsorbed. At the same time, binding force tigate the morphology structure of the samples before and after modi­
between the adsorbent and adsorbates were much stronger than that fication. Fig. 5A. Shows the XRD pattern results of UMCFA and Fig. 5B.
shows the result of MCFA. The results showed that UMCFA has more

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Fig. 2. XPS Analysis scans of Survey (A), Carbon (B), Oxygen (C), contents of UMCFA, MCFA, and loaded dyes with MCFA.

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Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

Fig. 3. SEM images of UMCFA (A), MCFA (B) and dye loaded (C) at 3.0 k magnification.

Fig. 4. BET analysis of UMCFA and MCFA.

and magnetite were also present in the MCFA (Taufiq et al., 2018). The
Table 2
XRD pattern results (Fig. 5B) found that the modification by HCl and
BET analysis of UMCFA and MCFA.
NaOH showed more amorphous and irregular porous structure than
Slope Intercept (1/ Correlation Constant Surface UMCFA. The modification by acid and base together increased the hy­
(1/g) g) coefficient (r) (C) area (m2/
droxyl group in the modified samples.
g)

UMCFA 696.187 7.750e+01 0.999 9.984 4.501

MCFA 250.026 8.013e+001 0.999 32.202 13.496 3.4. IR analysis of UMCFA, MCFA and dye loaded MCFA

peaks than MCFA on different degrees. Peaks of UMCFA indicate the The UMCFA is a pozzolana dusty material with potential activities, it
crystalline and spherical smooth structure of minerals. The smaller is a kind of aluminosilicate. The main components of UMCFA are silicon
peaks of MCFA results showed amorphous structure with more pores. dioxide (SiO2) and aluminum oxide (Al2O3). Fig. 6 shows the infrared
Furthermore, the surface volume has increased by HCl modification. The spectra of UMCFA, MCFA and dye loaded MCFA. In the infrared spec­
chemical modification with NaOH has more rough surface with more trum of UMCFA, the stretching vibration and in-plane bending vibration
porous structure (Astuti et al., 2019). But acid modification of CFA of OH group in water were caused at 3420 cm-1 and 1631 cm− 1. In
resulted into higher intensity of diffraction peaks. The major phases of MCFA, the intensity of the adsorption peak and the width of the region
CFA were resulted quartz and mullite but some minor phases hematite has increased, which indicates that more silanol hydroxyl groups are
formed on the surface of MCFA. In the infrared spectra of dye loaded fly

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Fig. 5. XRD patterns of UMCFA (A), and MCFA (B).

Fig. 6. IR curve of transmittance % of UMCFA, MCFA and dye loaded by MCFA.

ash, the intensity of this adsorption peak further increased, and finally were caused by the stretching vibration of C-N bond, C-O bond in dye
formed a wide and strong adsorption band in the region of 3450 ~ molecule and C = C bond in benzene ring. Generally, the infrared
3250 cm− 1. spectrum showed that the increase of silanol hydroxyl on the surface of
Furthermore, there were a lot of amino and hydroxyl groups in the modified MCFA is an important reason for the increase of its adsorption
dye molecules adsorbed by MCFA, which leads to the increased of capacity. Most of the dye molecules were combined with MCFA through
stretching vibration signal of N-H bond and O-H bond. Therefore, the hydrogen bond and Van der Waals force.(Fig. 7).
adsorbed dye molecules form a large number of hydrogen bonds with Moreover, the adsorption peak intensity of Si− O at 805 cm− 1 has
silanol hydroxyl groups on the surface of MCFA. The only exception was reduced with a blue shift of about 10 cm− 1 due to the coordination
KN-G loaded MCFA, whose adsorption peak intensity in the region of between Al3+ and Si− OH, which would weaken the symmetrical
3510 ~ 3360 cm− 1 is weakened, which may be due to the fact that KN-G stretching vibration of silicon hydroxyls. While the stretching vibration
is a chelating dye, and there are fewer hydrogen groups in its molecule,
so the hydrogen bonding force between KN-G and MCFA is weak.
In addition, the symmetric and antisymmetric stretching vibration of
C-H bond appeared near 2920 cm− 1 and 2850 cm− 1 in the infrared
spectra of all dye loaded fly ash, which did not exist in MCFA and
UMCFA. Because this peak corresponds to the vibration of methylene in
dyes molecular skeleton, it is another strong evidence for the adsorption
of MCFA. Finally, the infrared spectra of dye loaded fly ash showed
complex absorption bands in the region of 1520 ~ 1280 cm− 1, which Fig. 7. Surface structure of nano silica.

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of Si− O− Si and Si− O− Si, had a red shift to from 1062 cm− 1 to greater Van der Waals’ to the adsorbent, which led to a higher adsorp­
1105 cm− 1 due to the antisymmetric stretching vibrations of Si-O-Si tion. Furthermore, the MCFA have the loose and porous structure, that
bonds had been influenced by the rearrangement effects of Al3+ ions. increase the specific surface area. Furthermore, MCFA has more oxygen-
Those changes indicated that, after the acid-base modification, part of containing groups (Si-OH), which could form plenty of hydrogen bonds
Al2O3 components in CFA was transformed into Al(OH)3. Since the to the polarity group, such as hydroxy, amidogen and carboxyl in the
aluminum hydroxide was considered an efficient coagulant to the dye molecules. As a result, its adsorption to reactive dyes has also
organic pollutants in water (Mohammed et al., 2020). The formation of significantly increased.
Al(OH)3 could be another reason for the improved adsorption capacity As the dosage increased, the removal of the dyes also increased, but
of MCFA. The possible structure of surface silicon hydroxyl is shown in the Qe reduced due to the decreased utilization ratio, because Qe de­
Fig. 8. pends on concentration of dyes and dosage of adsorbent. The study
found that directive dyes adsorption was higher than reactive dyes due
to of ions exchange reaction. Azo dyes, triarylmethane dyes, anthra­
3.5. Adsorption measurements of MCFA quinone dyes, and heterocyclic compounds (Turquoise Blue X-GB, and
Brilliant Blue RL etc.) have cationic form that repels the cation of
Fig. 8 shows the adsorption isotherm and removal % of four dyes by adsorbent and reactive dyes has anionic form which repels the polar acid
MCFA adsorbent. Results confirmed that the adsorption of directive dyes group Si-O- and silicate anion present in the adsorbent (Chinoune et al.,
like direct fast scarlet 4BS and direct sky blue 5B was more than reactive 2016). But in this study all dyes having anions and adsorption reaction
dyes like acid navy blue R and reactive turquoise blue KN-G. The was recorded because of hydrogen bonding and Van der Waals force
adsorption (Q) of direct fast scarlet 4BS and sky blue 5B was between dyes and adsorbent.
18.460 mg g− 1 and 13.469 mg g− 1, respectively at initial concentration
(0.05 g dosage) of MCFA. But the adsorption of reactive dyes was lower 3.5.1. Adsorption isotherm
than directive dyes. The adsorption of acid navy blue R at 0.05 g dosage Fig. 9 shows the adsorption isotherm curve by different concentra­
of MCFA was 11.034 mg g− 1 and reactive turquoise blue KN-G was tion of dyes, in which different dye concentration (20 mg/L, 40 mg/L,
10.217 mg g− 1. 60 mg/L, 80 mg/L, 100 mg/L, 120 mg/L, 140 mg/L, 160 mg/L,
A higher concentration or more valences of anions present in reactive 180 mg/L and 200 mg/L) of each four dyes was used to check the
dyes solution decreased the adsorption as compare to directive dyes adsorption capacity at same adsorbent dose 0.05 g. Dye concentration
solution (Chinoune et al., 2016). Similarly, the dosage concentration effect the adsorption capacity, i.e., 20 mg/L concentration of dyes has
increased the removal % of dyes color and decreased the adsorption weaker bonding and can easily degrade than complex structures of dyes
capacity of dyes. The maximum removal percentage of dyes color was with higher concentration as 200 mg/L. Results showed that as the
recorded 98.48% for direct sky blue 5B at 0.05 g of MCFA dosage con­ concentration of dyes increases, Q also increases. However, lower con­
centration, and adsorption of this dye at same dosage concentration centration dyes can easily degrade, thus the Q was also increased as
decreased (3.939 mg g− 1). Similarly, the minimum removal % of dye compared to higher concentration dyes. The adsorption effect of low
color was recorded 25.52% for reactive turquoise blue KN-G at 0.05 g concentration dyes has more fluctuations than higher concentrations,
dose concentration of MCFA, but at this concentration of adsorbent due to the electrostatic interaction and chemical reactions between
dosage the adsorption capacity was increased (10.217 mg g− 1). Results adsorbent (0.05 g) and dyes concentration, which was higher on initial
found that directive dyes have more removal % as compare to reactive stage, but at higher concentration it was decreased and finally reached
dyes due to the difference in dyes’ structure, molecular weight, to equilibrium state.
hydrogen bonding and Van der Waals’ forces. Table 3, shows the adsorption Freundlich and Langmuir isotherm
Researchers found that the adsorption capacity of CFA could be models values that reflect the relationship between the adsorbate con­
influenced by its constituent and structure, and it has been considered centration and adsorbing capacity under certain temperatures, which
that its removal process of organic pollutants in water is complicated are associated with the factors, including surface and pore distribution
that includes adsorbing, coagulation and precipitation effects. properties of adsorbent, and their interaction to adsorbate. Table 3
The study found that MCFA has higher adsorption to direct dyes than shows that the adsorption of three dyes (direct sky blue 5B, acid navy
reactive dyes, that might due to their different molecular structures. The
direct dye has the lower molecular weights, lower conjugated systems
and less coplanarity. For these reasons, the direct dyes could have

Fig. 9. Effect of different concentration of dyes (mg/L) on the adsorption ca­

Fig. 8. Adsorption of different dyes by different dosage of MCFA. pacity Q (mg/g) by MCFA adsorbent.

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Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

Table 3
Isotherm parameters of adsorption of four different dyes using MCFA adsorbent.
Isotherms Parameters Direct Fast Scarlet (4BS) Direct Sky Blue (5B) Acid Navy Blue (R) Reactive Turquoise Blue (KN-G)

KL (L/g) 0.43 0.016826 0.005359 0.004736

Langmuir Q max (mg/g) 58.13953 55.5556 62.1118 31.64557
R2 0.9974 0.9095 0.6095 0.4229
KF((mg/g) (L/mg)1/n) 3.513807 1.400599 0.808965 0.657902
Freundlich nf 0.3371 0.6115 0.7735 0.7068
R2 0.8382 0.9918 0.9685 0.9235

blue R, and reactive turquoise blue) have good fittings to Freundlich adsorption rates on MCFA, which mainly depends on the molecular
model (R2 = 0.9918, 0.9684 and 0.9235, respectively), but the Lang­ structure of dyes, including molecular weight and polarity.
muir model fitting value for direct scarlet 4BS was R2 = 0.9974, which From the Table 4 and Fig. 10, the adsorption behaviors of four dyes
was above three dyes, indicating that both physical and chemical could be better described by pseudo second order kinetics (R2 = 0.9992,
adsorption properties were participated in the process. Freundlich and R2 = 0.9748, R2 = 0.9988, R2 = 0.9306) than pseudo first order kinetics
Langmuir model was applied to describe the adsorption capacity for the of four dyes respectively, which indicated the hydrogen bond associa­
highly reactive species of adsorbents, with large surface area and more tion among the MCFA surface oxygen-containing groups and polar parts
porous structure (Zhou et al., 2018). of dye molecules that plays an important role in the adsorption process.
MCFA has porous structure that increased the specific surface, which Furthermore, the pseudo second order kinetics model was considered
is a benefit for the dye molecules to approach the adsorption sites, where that represent the linear relationship of adsorption rate with concen­
the inter-molecular forces (Van der Waals’ force and hydrogen bond) trations of two reactants, including the adsorbate and adsorbent, the
played great role. On the other side, the increased oxygen-containing adsorbent dosage is an important factor to be consider. Previous study
groups of MCFA enhanced the H-bonds combinations to the polar stated that chemisorption process between the surface and adsorbate,
groups of dye molecules (-OH, -NH2, -COOH). in general, the adsorption the pseudo-second-order results were better than the pseudo-first-order
behaviors of dyes on the MCFA could be considered as a combined (Zhou et al., 2018). Pseudo first and second order kinetics (Zhou et al.,
process including both physical and chemical adsorptions. Langmuir 2015) can be expressed by following equations,
isotherm models’ the monolayer coverage of the adsorption surface / /
t
confirmed that adsorption occurred at specific homogeneous adsorption Pseudo − second − order： = t qe + 1 k2 q2e (6)
q
sites within the adsorbent and intermolecular forces decreases rapidly
when the distance from the adsorption surfaces increases (Xie et al.,
Pseudo-first-order：ln（qe-q）=lnqe-k1t (7)
2011).
Langmuir and Freundlich adsorption isotherm can be expressed by Note: t: adsorption time (min).
the following equations, q: adsorption (mg/g).
1 qe: equilibrium adsorption capacity.
Freundlich isothermal equation logqe = logKF + logCe (4) K2: The rate constant of pseudo-second-order.
n
K1: First order adsorption rate constant.
qe
Langmuir isothermal equation： = KL qmax − KL qe (5)
Ce
3.6. Adsorption comparison of MCFA with other adsorbents
Note：qe：adsorption（mg/g）.
Ce：the concentration of dye（mg/L）.
Adsorption comparison between MCFA with other regular adsor­
KL: adsorption coefficient（adsorption equilibrium constant）.
bents were analyzed to measure the MCFA efficiency and adsorption
KF: Freundlich adsorption coefficient.
capacity. Fig. 11 shows the removal efficiency (%) and adsorption ca­
pacity (Q) of MCFA and other regular’ adsorbents (carbon black, chi­
3.5.2. Adsorption kinetics mechanism
tosan, zeolite, starch and UMCFA) at the dosage of 0.05 g and 0.4 g each.
The adsorption kinetics was used to uncover the adsorption mecha­
Result confirmed that the adsorption capacity of carbon black, chitosan
nism and possible rate-determining step, which is expressed by the
and MCFA for direct fast scarlet 4BS dye was better as 4.687 mg g− 1,
retention time of adsorbate on the solid-fluid interface. From the kinetics
4.862 mg g− 1, and 4.873 mg g− 1, respectively at 0.4 g dosage of
curves, it was found that as the molecular weight of dyes has increased,
adsorbent. But at the lower dosage (0.05 g) of adsorbent the carbon
their adsorption equilibrium time also increased, that might be due to
black and chitosan results were better than MCFA. However, the MCFA
the higher molecular weight of dyes. Dyes with higher molecular weight
was found better than zeolite, starch and UMCFA, which can be due to
has weaker thermal motion capacity and greater steric hindrance, thus
the higher surface volume, volume by weight and porosity of carbon
difficult to reach the adsorption site. As a result, the Direct Fast Scarlet
black and chitosan as compare to MCFA.
（4BS and acid navy blue R has higher adsorption rate than direct sky
The removal percentage analysis of directive dyes at 0.4 g dosage
blue 5B and turquoise blue KN-G. Where, the reactive turquoise blue KN-
found that the MCFA and chitosan removal efficiency (97.47% and
G has the lowest adsorption rate. Different dyes have different
97.245%) was better than carbon black, but the reactive dyes (acid navy

Table 4
Pseudo-first-order and Pseudo-second-order model parameters for the adsorption of four dyes by using MCFA adsorbent.
Model Parameters Direct Fast Scarlet (4BS) Direct Sky Blue (5B) Acid Navy Blue (R) Reactive Turquoise Blue (KN-G)

k1 10− 2(1/min) 2.34 0.72 3.38 3.15

Pseudo-first-order qe（mg/g） 15.367 14.466 5.963 31.397
R2 0.9597 0.9612 0.946 0.8997
K210− 3 (g/mg/min) 4.374 2.003 -72.109 6.291
Pseudo-second-order qe（mg/g） 39.370 26.385 23.095 17.036
R2 0.9992 0.9748 0.9988 0.9306

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Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

Fig. 10. Effect of contact time and Pseudo-second-order of different four dyes by MCFA adsorbent.

Fig. 11. Adsorption capacity (Q) (mg/g) and removal efficiency (%) comparison of different adsorbents (MCFA with Carbon black, starch, zeolite, chitosan and
UMCFA) at 0.05 g dosage (A) and 0.4 g dosage (B) for dyes colors.

blue R, reactive turquoise blue KN-G) results showed that the removal
efficiency of carbon black (96.576% and 92.953%) was better than
MCFA and chitosan. Previous study confirmed that the removal effi­
ciency of combined application of chitosan and MCFA for reactive red
dye adsorption was 88.8% (Mohammed et al., 2020), The removal ef­
ficiency of reactive turquoise blue KN-G dye by just chitosan was found
96.541% which was greater than MCFA and carbon black. Results for
the other three adsorbents showed that zeolite was the weakest adsor­
bent of dyes. Removal efficiency % trend of all adsorbents at the dosage
0.4 g for the selected dyes i.e. direct fast scarlet 4BS and direct sky blue
5B was MCFA˃ Chitosan˃ CB˃ UMCFA˃ Starch˃ Zeolite, MCFA˃ Chi­
tosan˃ UMCFA˃ CB˃ Starch˃ Zeolite, respectively, and, acid navy blue R
and reactive turquoise blue KN-G followed the trend order as CB˃ Chi­
tosan˃ MCFA˃ UMCFA˃ Starch˃ Zeolite and Chitosan˃ CB˃ MCFA˃
UMCFA˃ Starch˃ Zeolite, respectively.

3.7. Effect of different pH on the adsorption

In order to simulate the treatment of printing and dyeing wastewater

with simulated fly ash, adsorption experiments were carried out under
different pH values. It can be seen from Fig. 12 that the adsorption ca­
pacity of MCFA for the four dyes were increased with the increase in pH Fig. 12. Effect of different pH on different dyes by MCFA.
value. At pH = 9 value, the adsorption capacity of MCFA for the dyes has
reached the maximum adsorption. The reason can be explained by the
aggregation state of dye molecules in water.
When the pH is low, the dissociation degree of sulfonic group in dye

10
Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

molecules is small, and most of them exist in the form of -SO3H. Table 5
Therefore, there is strong hydrogen bonding between dye molecules, Specific Composition of prepared industrial waste-water.
and it is easy to form aggregates. After the formation of aggregates, the Simulated wastewater composition Contents
dimension and steric hindrance size increases, the movement ability
Dyes Disperse yellow RG-FL
decreases, and the binding ability with fly ash decreases, so it is not easy Disperse blue E-4R
to be adsorbed on the surface of MCFA. With the increase of pH, the Disperse red S-5BL
dissociation degree of sulfonic group in dye molecules increased, and Direct blue 5B
gradually transformed into-SO3Na form. The dye molecules change into Direct red 4BS 100 mg/L
Active green KE-4B
anions, and the repulsion between them increases, which makes the Active red K-2 G
aggregates depolymerize. Monomolecular dyes are easier to be adsorbed Active blue KN-R
on the surface of MCFA, which increases the adsorption capacity. Sizing agents
However, if the pH is too high, the silanol hydroxyl on the surface of PVA 1 g/L
Soluble starch 1 g/L
MCFA will deprotonate and change to alkoxide, which will increase the
CMC 0.5 g/L
electrostatic repulsion between MCFA and dye molecules, so the
adsorption capacity will decrease. In general, the MCAF shows the
maximum adsorption capacity when it is weakly alkaline (pH = 9), increases continuously. In the range of dosage from 10 ‱ to 20 ‱,
which is also very close to the pH value of real printing and dyeing MCFA has higher COD and sludge removal rates for simulated waste­
wastewater, thus proving MCFA good in application prospect. water, indicating that MCFA has better removal ability for colloidal
substance, suspended solids and water-soluble pollutant in wastewater.
The mechanism may include the combined action of coagulation,
3.8. Application for simulated textile industrial waster
adsorption and precipitation. But at the same time, it can also be seen
that with the increase of dosage, the sludge production after treatment
The production process of textile printing and dyeing is very com­
will also increase correspondingly. The increase of sludge quantity will
plex. Dyestuff, auxiliaries, sizing agent and other substances are used in
increase the difficulty of follow-up treatment, energy consumption and
a large number of varieties and quantities, which leads to the complex
cost of the treatment. Therefore, according to the experimental results,
composition of printing and dyeing wastewater. Printing and dyeing
the recommended dosage of MCFA is between 10 ‱ to 20 ‱.
wastewater contains a lot of organic pollutants, including various
organic substances in colloidal, suspended and dissolved forms. It is
difficult to determine these organic compounds directly, so the 3.9. Regeneration of MCFA adsorbent
comprehensive indicator, COD, is generally used for evaluation. In the
standards of many independent countries and regions, the removal rate Regeneration is another important factor to evaluate the perfor­
of COD and chromaticity is also used to evaluate the treatment effect of mance of adsorbent. The regeneration is to desorption, the adsorbed
printing and dyeing wastewater. material with some method under the condition that the structure of the
Therefore, a simulated printing and dyeing wastewater was prepared adsorbent itself does not change or rarely changes, so as to achieve the
by using various dyes, auxiliaries and sizes. Its composition and con­ purpose of reuse. There are many ways to regenerate adsorbents. As an
centration were similar to cotton textile dyeing industrial wastewater, inorganic adsorbent, MCFA has good chemical stability, mechanical
and the COD content was about 4320 mg/L. The Fig. 13 result shows strength and thermal stability, which is easy to regenerate. This is an
that if the dosage of adsorbent increased, as the removal % of COD advantage of MCFA over organic adsorbent due to its low stability
increased, but the sludge quantity also increased, so that maximum (Karmakar et al., 2017). In this paper, the heating regeneration method
removal % of COD at 20 ‱ dosage concentration and the sludge was used to regenerate the MCFA, and the influence of different tem­
quantity also not higher. The specific composition is shown in the peratures (200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, and 700 ℃) on the
Table 5. adsorption properties of the regenerated MCFA was investigated. Fig. 14
Fig. 13 shows the actual effect of MCFA with different dosage on the results shows that at 300 ℃ temperature MCFA adsorbent can be
treatment of the simulated printing and dyeing wastewater. It can be regenerate and reuse as many cycles.
seen that with the increase of the dosage, the COD removal rate of MCFA It can be seen from Fig. 14 that with the increasing heating tem­
perature, the adsorption capacity of regenerated MCFA first increases,
and has best adsorption effect on 4BS at 300 ℃. After300 ℃, the

Fig. 13. Effect of MCFA adsorbent on COD and sludge quantity in indus­ Fig. 14. Regeneration of MCFA adsorbent at different temperature and recy­
trial wastewater. cling of MCFA at 300 ℃.

11
Z. Hussain et al. Journal of Hazardous Materials 422 (2022) 126778

adsorption performance of regenerated MCFA gradually decreased with CRediT authorship contribution statement
increasing temperature. The result shows that the decomposition of
most dye molecules is mainly found in the temperature range of 300 ~ Zawar Hussain: Conceptualization, Writing − original draft prepa­
400 ℃. In this range, the first is the dehydration and deamination re­ ration, Methodology. Wang Haitao: Supervision, Funding. Hao Zhang:
action between functional groups. At higher temperature, the aromatic Writing − review & editing. Na Chang: Writing − review & editing.
ring and carbon chain on the molecular skeleton of dye molecules break Jingqiu Sun: Writing − review & editing. Simeng Xiang: Software,
and decomposed, Volatile hydrocarbon compound is released. In this Visualization. Tehreem Ayaz: Reviewing, Editing, Visualization,
process, the organic structure of the dye molecules is degraded, resulting Formatting.
in some quality loss (Mahapatra et al., 2018). The other part forms
inorganic compound with high thermal stability and remains in the
Declaration of Competing Interest
surface and pore canal of fly ash adsorbent. Therefore, at 300 ℃ most of
the organic components in the dye molecules adsorbed by MCFA were
The authors declare that they have no known competing financial
degraded, resulting in a significant reduction in its mass. At the same
interests or personal relationships that could have appeared to influence
time, a certain number of polar groups, such as silanol hydroxyl,
the work reported in this paper.
carbonyl and carboxyl groups, remain on the surface of MCFA. These
adsorption sites were reactivated at high temperature, making MCFA
capable for adsorption again. However, at higher temperature (500 ~ Acknowledgment
700 ℃), oxygen-containing groups on the surface of fly ash decomposed
and the residual part of dye molecules forms heat-resistant inorganic The Authors would like to express their sincere gratitude with Na­
compounds at high temperature and remains in the surface or pores of tional Key R&D Program of China (2019YFC0408400), Tianjin Key
fly ash, resulting in the reduction of adsorption capacity of regenerated Science and Technology Program Foundation (19PTZWHZ00030,
fly ash. 19YFSLQY00060).
At the same time, the regenerated MCFA at 300 ℃ still has good
adsorption capacity after three cycles. Based on this, in this study, Conflict of interest
300 ℃ was used as the optimal regeneration temperature of MCFA.
The authors have no conflict of interest.
4. Conclusion
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