See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/354167121

Sudan black B dye degradation in aqueous solution by Fenton oxidation

process: Kinetics and cost analysis

Article in Case Studies in Chemical and Environmental Engineering · August 2021

DOI: 10.1016/j.cscee.2021.100126

CITATIONS READS

45 337

5 authors, including:

Md. Burhan Kabir Suhan S M Tanveer Mahtab

Bangladesh University of Engineering and Technology Texas Tech University
18 PUBLICATIONS 537 CITATIONS 2 PUBLICATIONS 45 CITATIONS

SEE PROFILE SEE PROFILE

Wafi Aziz Md. Shahinoor Islam

Bangladesh University of Engineering and Technology Bangladesh University of Engineering and Technology
1 PUBLICATION 45 CITATIONS 104 PUBLICATIONS 4,355 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Md. Burhan Kabir Suhan on 03 September 2021.

The user has requested enhancement of the downloaded file.

 Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Contents lists available at ScienceDirect

Case Studies in Chemical and Environmental Engineering

journal homepage: www.sciencedirect.com/journal/case-studies-in-chemical-
and-environmental-engineering

Sudan black B dye degradation in aqueous solution by Fenton oxidation process: Kinetics and
cost analysis

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

Keywords The presence of dyes in effluents discharged from the textile industries is one of the major concerns of water-
Fenton living organisms. This study aimed at investigating the Fenton degradation of Sudan black B (SBB) dye in an
Wastewater aqueous solution. The effects of initial dye concentration, Fe2+ concentration, and H2O2 concentration were
Sudan black B
evaluated based on the removal of color and dye from the solution. Operating costs and kinetics study of the
Dye degradation
Operating costs
Fenton process were assessed. The optimum conditions were determined as [Fe2+] of 150 mg.L− 1, [H2O2] of 100
Kinetics mg.L− 1, and a reaction time of 30 min. Dye and color removals for the different combinations of the process were
on average > 80% and >75%, respectively. However, the process was not effective for the excess amount of Fe2+
and H2O2 due to their scavenging effect on hydroxyl radicals (•OH). The degradation process of SBB dye fol­
lowed a pseudo-second-order kinetic model, and the rate constant was varied from 0.0012 to 0.0036 g.mg− 1.
min− 1 for the dye adsorption range of 333–769 mg.g− 1. The total operating costs were found in the range of
$1.78–6.28 per kg of dye removal in 1 m3 of wastewater. Finally, the outcome of this study proved that the
Fenton process is a good option for the treatment of dye-containing wastewater for the sustainable development
of the textile industries.

1. Introduction [17–19]. High toxicity textile wastewater inhibits biological treatment

steps [20,21], and chemical coagulation produces a large volume of
Textile wastewaters contain a large number of refractory and toxic sludge [22]. Electrocoagulation has many advantages, but it depends on
organic compounds (i.e. synthetic dyes) that significantly affect the the electrical energy entirely, consumes sacrificial anode, and the pas­
exposed environment. To attain sustainable development of textile sive film formation reduces the efficiency of the process [16]. On the
sector, the treatment of large volumes of wastewater has become a very other hand, adsorption, ion exchange, ultraviolet photolysis, and AOPs
crucial issue in recent years [1]. It is found that about 10–15% of the are relatively costly despite their satisfactory contaminants removal [23,
synthetic dyes used in textile manufacturing processes are lost in 24].
effluent streams [2]. These effluents create environmental problems and Compared with other AOPs, researchers explored that the Fenton
pose a tremendous potential toxic threat to ecological and human health process is the most popular for its high performance and simplicity to
(Shuchi et al., 2021). Regulatory bodies of developing countries like oxidize the organic compounds as well as its non-toxicity behavior [25,
Bangladesh, China, India, etc., are unconscious about the treatment 26]. In addition, required reagents are also readily available, easy to
process and consequences of disposing of the wastewater from textile store, handle and environmentally safe [27] Both ferrous and ferric ions
industries to surface water after improper or without treatment [3]. generated in the Fenton process are coagulants [28], hydroxide com­
Aerobic degradation of these dyes is inadequate, and anaerobic pro­ pound formation can also act like adsorbent [29]. Therefore, it has three
cesses produce potential carcinogenic aromatic amines that cause functions of oxidation, coagulation, and adsorption in the treatment
long-term health concerns [4]. Therefore, removing the dyes from the process. However, Fenton has some inherent disadvantages which limit
textile industries is a subject of interest for regulatory authorities, aca­ its application and promotion [30]. For example, strict pH range, high
demicians, and environmentalists. H2O2 consumption, and ferric sludge accumulation affect the oxidation
Commonly applied environmentally-friendly treatment methods for efficiency [26,28,31].
wastewater treatment consist of various processes involving biological Sudan dyes are extensively used in the textile manufacturing in­
[5–7], physicochemical [8,9], membrane (Rambabu et al., 2016; [10], dustry. Aquatic lives are adversely affected by the wastewater produced
electrochemical (Sahu 2019; [3], adsorption (Islam et al., 2018; [11,12], from these types of industries [32] resulting a detrimental effect on
advanced oxidation processes (AOPs) [13,14] and combined processes humans from the consumption of seafood SBB dye biodegradation has
[15,16]. AOPs are a set of chemical treatment methods to remove been studied previously in processes like Photocatalysis [33], microbial
organic (generally) and inorganic (sometimes) materials in wastewater [34], adsorption (Sun et al., 2015), UV/H2O2 (Ember et al., 2010), etc.
by oxidation through reactions with hydroxyl radical (•OH). This •OH In the past few decades, Fenton, photo-Fenton and electro-Fenton pro­
can be generated from chemical (e.g., Fenton, ozonolysis), electro­ cesses have been reported in several reviews and books for different
chemical (e.g., electro-Fenton), and photochemical (e.g., photo-Fenton, types of dye removal [35]; Nidheesh and Gandhimathi, 2012; Pariente
photocatalytic degradation, ultraviolet photolysis) methods, etc. et al., 2013; [36–38], but to the best of our knowledge, no other research

https://doi.org/10.1016/j.cscee.2021.100126
Received 15 April 2021; Received in revised form 14 August 2021; Accepted 25 August 2021
Available online 27 August 2021
2666-0164/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

study has been performed for the degradation of SBB by the Fenton auto-decomposition of H2O2 appears at high pH and thus, the activity of
process. Fenton reagent is reduced with increasing pH due to the lack of active
Therefore, the study considered optimizing the degradation of SBB Fe2+ where the produced inactive iron oxyhydroxides and ferric hy­
dye using the Fenton process to address the treatment of a large quantity droxide are precipitated [41]. Thus, the efficiency of the Fenton process
of textile wastewater which is discharged after ineffective or without to degrade organic compounds is reduced both at high and low pH. Most
treatment in most of the developing countries. The generated •OH and of the researchers suggested taking pH > 2.7 and < 3.5 (Fischbacher
HO2• radicals from the Fenton process react with dye fastly and can et al., 2017; [41]. In the current study, pH was selected at 3 for the
mineralize the dye to CO2 and H2O [39,40]. The findings from the study efficient degradation of dye concentration and color.
will significantly assist the readers to correlate the dye degradation and Dye concentrations in textile wastewaters are varied in a wide range
cost required per unit dye in a Fenton process with other treatment with a typical concentration range of 40–100 mg.L− 1. Therefore, 50, 70
methods. Thus, the main objective of this research was to investigate the and 100 mg.L− 1 dye concentrations were selected for the current study
degradation of SBB dye using the Fenton process. The other objectives [3,42]. According to previous research, effective degradation was found
were: optimization of the dosage of Fe2+ to degrade SBB dye at different while Fe2+ and H2O2 concentration were in the range of 25–300 mg.L− 1
concentrations, optimization of the dosage of H2O2to degrade SBB dye at and 50–600 mg.L− 1, respectively (Neppolianet al., 2004;Yalfani et al.,
different concentrations, study of the degradation kinetics of SBB dye, 2009; [43,44]. Therefore, in the current study, experiments were carried
andoptimization of the operating costs for the effective degradation of out to evaluate mainly three findings consist of (a) Effect of initial Fe2+
SBB dye for different dosage of Fe2+ and H2O2. The performances of the concentration, b) effect of initial H2O2 concentration, and c) effect of
Fenton processes were evaluated based on dye and color removal. initial dye concentration. Finding (a) was conducted under 50, 100, 150,
and 200 mg.L− 1 of Fe2+, while H2O2 concentration was kept constant at
2. Materials and methods 100 mg.L− 1, finding (b) was conducted under 100, 200, 300, and 400
mg.L− 1 of H2O2, while Fe2+ concentration was kept constant at 100 mg.
2.1. Materials L− 1 and finding (c) was conducted for 50, 70 and 100 mg.L− 1 of dye
concentration.
All chemicals and reagents such as Sudan Black B(also known as During the experiment, sequentially four samples of 10 mL were
Solvent Black 3) dye (formula C29H24N6, dye absorption ≥20,000 at taken at 15 min intervals and the last sample was taken after 120 min.
596–603 nm in ethanol, molar mass 456.54 g/mol), H2O2 solution [30% The speed of the mixing was selected at 80 rpm. Every sample was
(w/v)], sodium acetate (C2H3NaO2), sodium hydroxide (NaOH), ferrous allowed to settle for about 5 min before filtration. The samples were
sulfate (FeSO4.7H2O) were purchased from Sigma Aldrich. Reagent filtered using a 0.45 μm nylon filter to remove coagulated substances.
grade sulfuric acid (H2SO4) was used to maintain pH. All the solutions Since SBB dye is mostly used for its lucrative color property, for analysis
were prepared using demineralized water. The structure of Sudan Black color and dye concentration were selected. The absorbance and color of
B dye is shown in Fig. 1. the samples were analyzed using SHIMADZU UV-2600 UV–Vis Spec­
trophotometer and HACH DR6000TM UV–Vis Spectrophotometer,
respectively. The maximum peak of SBB dye was observed at 598 nm
2.2. Methods wavelength. Therefore, absorbance was measured at this wavelength,
and the color was measured in the Co–Pt unit. The dye removal % was
2.2.1. Preparation of wastewater determined using the following equation [12,45]:
500 mL of dye solution of each concentration (50 mg.L− 1, 70 mg.L− 1,
and 100 mg.L− 1 dye) was prepared before each experiment.The initial % ​ removal =
C0 − Ce
× 100
pH of sample water was adjusted to the desired value 3 with 6 N H2SO4, C0
where the buffer solution of NaOH and C2H3NaO2 was added to main­
where Co (mg.L− 1) and Ce (mg.L− 1) are the initial dye concentration and
tain the pH around 3. The prepared dye solution was then treated.
equilibrium dye concentration, respectively.
2.2.2. Experimental
2.3. Degradation kinetics
The dye degradation experiment was performed using a beaker (as a
reactor) equipped with a glass bar. A predetermined amount of solid
The kinetics of the degradation of SBB dye by different combinations
FeSO4.7H2O and H2O2 solution was added. All experiments were carried
of Fe2+ and H2O2 in the Fenton process was studied for zero-order, first-
out at room temperature ranged from 22 to 25 ◦ C. These steps were
order, second-order, pseudo-first-order, and pseudo-second-order
repeatedly done for several parametric changes to assess the effects on
models with respect to time. During the calculation of pseudo-first-
absorbance and color removal efficiency.
order and pseudo-second-order, it was assumed that all SBB dye
The schematic of the reactor configuration is shown in Fig. 2. The
removal was happened due to adsorption on the iron oxide flocs. The
oxidation potential of the generated radicals (i.e., •OH) increases with
expressions for the above specified kinetic models are presented as fol­
decreasing pH [27], however, iron complex species [Fe(H2O)6]2+ and
lows (Eqns. (1)–(6)) [46,47]:
stable oxonium ion [H3O2]+ may form at very low pH values, which
Zero-order kinetics:
reduces the reactivity between Fe2+ and H2O2. In addition,
C − Co = k o t (1)
First-order kinetics:
C0
ln = k1 t (2)
C
Second-order kinetics:
1 1
− = k2 t (3)
C C0
Pseudo-first-order kinetics:

Fig. 1. Sudan Black B dye structure.

2
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Fig. 2. Schematic diagram of the Fenton oxidation process.

V(C0 − Ce )
Qe = (4) Po d 5 N 3 ρt
m Pw = (8)
1000CMO XV
ln(Qe − Qt ) = ln ​ Qe − k3 t (5)
d2 N ρ
Pseudo-second-order kinetics: Re = (9)
μ
t t 1
= + (6) where, Po is the power number (unitless, calculated from power number
Qt Qe k4 Q2e
chart with Re), Re is Reynolds number [48], N is the speed of rotation
where k0 (mg.L− 1.min− 1), k1 (min− 1), k2 (mg− 1.L.min− 1), k3 (min− 1) and (1.33 s− 1), d is impeller diameter (0.35 m), ρ is the density of the water
k4 (g.mg− 1.min− 1) represent the apparent kinetic rate constants of zero, (kg.m− 3), μ is the viscosity of the water (Pa.s), t is the treatment time (h),
first, second, pseudo-first and pseudo-second-order model respectively. CMO is the initial dye concentration (kg.m− 3) and X is the fraction
Co (mg.L− 1), C (mg.L− 1), and Ce (mg.L− 1) are the initial dye concen­ removal for the treatment time and V is the volume of wastewater (m3).
tration, dye concentration at time t (min), and equilibrium dye con­
centration, respectively. Qe and Qt is the amount of dye absorbed in mg. 3. Results and discussion
g− 1onto a unit mass of Fe2+ at equilibrium and at time t, respectively,
where m(g) is the mass of the adsorbent added in V(L) volume of treated 3.1. Effect of initial H2O2 concentration on color and dye
solution. It is to mention that pseudo-first-order parameters, Qe (exp.)
and Qe (calc.) are found from experimental data and fitted straight line H2O2 plays a crucial role in the Fenton process, as it is the main
equation, respectively. source of hydroxyl radical (•OH). Since H2O2 is considered as one of the
major expenses of the Fenton process, excess amount of it not only raises
2.4. Cost analysis the cost of the treatment but also decreases the treatment efficiency
[49]. From Table 2 (Eqn. 17) it can be seen that an excess amount of
Cost analysis is a very effective medium to compare different types of H2O2 can act as •OH scavenger causing a reduction in the performance
processes and to implement change in a process variable. In this study of the process.
cost analysis has been performed for operating costs only to compare the •OH + H2O2 → H2O + HO2• (10)
different combinations of the Fe2+/H2O2 ratio. The operating cost of the
Fenton process has been evaluated based on power cost, chemical con­ The influence of H2O2 dosage on the degradation of SBB dye was
sumption, and other parameters for the treatment of 1 m3 wastewater monitored by maintaining a constant 100 mg.L− 1 concentration of Fe2+.
per kg dye removal. Costs of the chemicals, power and others were Previously, it was found that 100 mg.L− 1 concentration of H2O2 has
collected from previous literature studies [3]. The total operating cost better removal efficiency in Fenton and Fenton-like processes than lower
(OC) includes power cost of mixing, chemical consumption cost and concentration value [50,51]. Thus, in this study concentration of H2O2
other costs like labor, maintenance, etc. (Eqn. (7)). was selected 100, 200, 300, and 400 mg.L− 1 to improve the efficiency as
well as to evaluate the optimum dosage of H2O2 among them. However,
OC = a × Pw + b × Ch + other costs (7) in all the conditions, the effect of a particular dosage of H2O2 was found
− 3 − 1
Where, OC is the operational cost ($ m .kg dye removal), Pw is the insignificant as similar decolorization and dye removal efficiencies were
energy consumption by the impeller (kWh.m− 3kg− 1 dye removal), Ch is observed in all concentrations of H2O2. From Fig. 3 it can be seen that
the chemical consumption (kg.m− 3kg− 1 COD removal). Coefficients a the trend of degradation of color and dye concentration was similar to all
and b are the prices of power cost ($.kWh− 1) and chemicals ($kg− 1), the curves that nearly coincided with each other.
respectively. Pw was calculated using the Eqns. 8-9 [48]. From Table 1 it can be seen that for the same dye and the same
concentration of Fe2+ (100 mg.L− 1), a few percentage degradations of
color and concentration were increased by increasing H2O2. This is due

3
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Fig. 3. Effect of initial H2O2 concentration on color and dye removal keeping constant concentration of Fe2+ (100 mgL− 1); a) and b) 50 mgL− 1 dye; c) and d) 70
mgL− 1 dye; e) and f) 100 mgL− 1 dye. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

to the increasing concentration of one or more reactants (i.e. •OH from

H2O2), the frequency of effective collisions to occur in a reaction will Fe2+ + •OH → Fe3+ + OH− (11)
also be high. Since the lifetime of hydroxyl radicals is very short (only a
2+
few nanoseconds), they can only react where they are formed. Thus, Besides at lower Fe dosage, the reaction solution was almost
increasing the concentration of H2O2 increases the probability of colli­ transparent. An increase in the dosage of Fe2+ turbidity in the reaction
sion between oxidizing species and organic compounds, leading to an mixture was observed. Previously, Gomathi [56] reported that the
increase in dye and color removal efficiency [4,52]. However, their costs excess concentration of Fe2+ form hydroxide compound (basic in na­
were very high compared to 100 mg.L− 1 H2O2 in operation due to the ture) rising the pH of the solution, which further leads to precipitation
additional cost of H2O2 (Table 1). Thus in this process, the optimum and thus, reduced the degradation rate of methyl orange dye. Most of the
dosage of H2O2 was found 100 mg.L− 1, and the effect of increasing H2O2 rate constants of Table 3 also increased as the concentration of Fe2+ rises
concentration to degrade color and dye concentration of SBB dye had no from 100 mg.L− 1 to 150 mg.L− 1. Thus, it can be concluded that the
significant impact after 100 mg.L− 1. The decolorization and removal degradation rate of SBB dye increased up to a certain concentration of
concentration at this dosage was found in between 35 and 85% and Fe2+. In this process, the optimum dosage of Fe2+ was found at 150 mg.
66–95% respectively (Table 1). For the degradation of 2,4-dichlorophe­ L− 1. The decolorization and dye concentration removals at this dosage
nol [53], obtained 580 mg.L− 1 H2O2 to be optimum at pH 2.5. were found in between 78 and 85% and 87–95%, respectively (Table 1).
However, in the previous degradation study of different dyes, optimum
initial Fe2+ concentration varied significantly based on the selection of
3.2. Effect of initial Fe2+ concentration on color and dye removal compound to be treated. For example [53], obtained 20 mg.L− 1 in his 2,
4-dichlorophenol degradation study while [57] found 280 mg/L in
The concentration of Fe2+ is one of the critical parameters in the p-hydroxybenzoic acid degradation.
Fenton processes. An increase in the dosage of Fe2+ from 50 mg.L− 1 to
200 mg.L− 1 has a pronounced effect on the efficiency of the process. The
influence of Fe2+ dosage on the degradation of SBB dye was monitored 3.3. Effect of initial dye concentration
by maintaining a constant 100 mg.L− 1 concentration of H2O2. At Fe2+
dosages of 50–150 mg.L− 1, a rapid increase of discoloration, and The effect of the Fenton process as a function of the initial concen­
removal of the dye was achieved on 30 min of treatment (Table 1). On tration of dye was evaluated. Figs. 3 and 4 show the changes in SBB dye,
the further increase of Fe2+ dosage to 200 mg.L− 1 from the 150 mg.L− 1 color and concentration with the reaction time, where Fig. 5 and Table 1
degradation rate decreases due to the inhibition effect of the Fe2+ show the removal efficiencies. The results indicated that for every same
(Fig. 4). These results are in accordance with the Eqn. 12 (Table 2) condition of Fe2+ and H2O2 concentration when the initial dye con­
where excess Fe2+ acts as a hydroxyl radical scavenger [54,55]. centration was increased from 50 to 100 mg.L− 1 removal efficiency of

4
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Table 1
Fenton process performances and cost analysis.
Dye Conc. Fe2+ H2O2 Color removal efficiency, % Dye conc. removal Cost analysisa Basis: 1 m3 wastewater per kg dye removal in 30 min
Conc. Conc. efficiency, % treatment

After 30 After 120 After 30 After 120 Power ($ × Fe2+ H2O2 Other costs Total cost
min min min min 104) ($) ($) ($) ($)
1 1
50 mg.L− 50 mg.L− 100 mg. 50 61 77 82 4.85 0.57 0.86 1.63 3.06
100 mg. L− 1 73 80 85 90 4.39 1.03 0.78 1.48 3.29
L− 1
150 mg. 85 88 95 98 3.93 1.38 0.70 1.33 3.41
L− 1
200 mg. 75 80 93 97 4.01 1.88 0.71 1.35 3.95
L− 1
100 mg. 200 mg. 74 80 86 91 4.33 1.02 2.03 1.46 4.51
L− 1 L− 1
300 mg. 76 82 89 91 4.21 0.99 2.96 1.42 5.37
L− 1
400 mg. 77 84 90 92 4.16 0.98 3.90 1.40 6.28
L− 1
− 1 − 1
70 mg.L 50 mg.L 100 mg. 45 55 69 70 5.39 0.45 0.68 1.30 2.43
100 mg. L− 1 69 75 78 79 4.78 0.80 0.60 1.15 2.55
L− 1
150 mg. 78 85 90 93 4.15 1.04 0.52 1.00 2.57
L− 1
200 mg. 76 83 86 92 4.32 1.45 0.55 1.04 3.03
L− 1
100 mg. 200 mg. 74 78 81 82 4.64 0.78 1.17 1.12 3.07
L− 1 L− 1
300 mg. 77 80 83 85 4.53 0.76 1.71 1.09 3.56
L− 1
400 mg. 78 81 84 86 4.44 0.74 2.24 1.07 4.06
L− 1
− 1
100 mg. 50 mg.L 100 mg. 35 45 66 68 5.65 0.33 0.50 0.95 1.78
L− 1 100 mg. L− 1 67 71 76 79 4.95 0.58 0.44 0.83 1.85
L− 1
150 mg. 79 83 87 90 4.30 0.76 0.38 0.73 1.86
L− 1
200 mg. 69 75 84 89 4.43 1.04 0.39 0.75 2.18
L− 1
100 mg. 200 mg. 67 74 77 78 4.85 0.57 0.86 0.82 2.24
L− 1 L− 1
300 mg. 72 76 78 80 4.76 0.56 1.26 0.80 2.62
L− 1
400 mg. 73 78 80 82 4.67 0.55 1.65 0.79 2.99
L− 1
a 5
costing data extracted from Refs. [3,49] study: Power cost: 0.06 $/kWh; FeSO4 .7H2O cost: $ 8.8 × 10− g− 1; H2O2 cost: $ 3.3 × 10− 4
g− 1; Other costs: Maintenance
cost: $ 0.003 m− 3 & Labor cost: $ 0.06 m− 3.

both color and dye decreased. The color and dye removals were 50–85% 3.4. Cost analysis for the different combinations of Fe2+/H2O2 in the
and 77–95% for 50 mg.L− 1 dye, 45–78% and 69–90% for 70 mg.L− 1dye, Fenton process
35–79%, and 66–87% for 100 mg.L− 1 dye, respectively. Similar result
has also been found by [58]. This decreasing concentration removal The average dye and color removals for the different combinations in
effect of dye was probably due to the non-availability of a sufficient the Fenton process were higher than 80% and 75%, respectively. It can
number of •OH to react with dye as the dye concentration increased [54, be seen from Table 1 that operating costs were affected by power cost to
59]. An important effect of initial dye concentration is also noticed in run mixer, chemical consumption cost, other costs (maintenance, labor
Table 3 that the rate constant decreased gradually for all orders when costs) and were in the range of 1.78–6.28 $/kg dye removal from 1 m3 of
dye concentration increased except zero order. For the treatment of wastewater. The treatment time was considered 30 min to evaluate the
pharmaceutical wastewater [60], obtained 74% TOC removal for the cost as >90% of total removal of color and dye was achieved within this
ratio of H2O2/Fe to be 150 (2500 mg.L− 1 H2O2). time. Moreover, we can see that the contribution of the power cost of
[61] applied a combined Fenton process in the degradation of 50 mg. mixers to the total cost is very little compared to any other costs due to
L− 1 reactive yellow 45 dye in an aqueous solution and reported the short reaction time of operation.
maximum dye removal of 95% within 240 min of treatment [61]. Chemical consumption cost was the prime operational cost due to the
Meanwhile, in this study, 98% removal of SBB dye was found within 50 higher cost of H2O2 ($ 3.3 × 10− 4 g− 1) and Fe2+ ($ 8.8 × 10− 5 g− 1) even
min for a 50 mg.L− 1 dye concentration (Table 1). Moreover, dyes in in bulk amount [3,49]. The most effective process condition based on
industrial effluent can be biodegradable but some recalcitrant com­ the cost analysis was found for 100 mg.L− 1 of dye, 50 mg.L− 1of Fe2+,
pounds remain after treatment which can be degraded further using the and 100 mg.L− 1 of H2O2 (1.78 $) while dye and color removals at this
Fenton process in integration [62,63]. Therefore removal efficiencies of condition were very less (color 35%, dye 66%) (Table 1). Thus, this
dye can be increased adequately if the Fenton process is performed after condition isn’t effective for the textile industry in reality. However, at
simplistic pretreatment of dyes using biological process. the condition of 100 mg.L− 1 dye, 150 mg.L− 1 of Fe2+, and 100 mg.L− 1 of
H2O2, the dye (87%), and color (79%) removals were acceptable. This
condition also has the highest capability to remove color among all other
conditions stated in Table 1. The cost for 1 m3 wastewater treatment at

5
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Table 2 addition of biological process as pretreatment can be very effective to

Mechanism and rate constants of Fenton process to degrade organic dye. treat textile industry wastewaters whenever the cost criteria will be one
Steps Reaction Equation Rate of the major concerning factors.
number constant
(M− 1. 3.5. Kinetic study
s− 1)

Chain initiation (Fe3+ Fe2+ + H2O2 ⎯⎯→ Fe3+ + (10) 40–80 Kinetic study of SBB dye degradation for zero-order, first-order,
generation) OH− + •OH second-order, pseudo-first-order, and pseudo-second-order models were
Fe3+ reduction by excess Fe3+ + H2O2 ⎯⎯→ Fe2+ + (11) 9.1 ×
H2O2 HO2• + H+ 10− 7
carried out. It was performed under six different conditions where Fe2+
Rate determining steps Fe2+ + •OH ⎯⎯→ Fe3+ + (12) 2.5–5 × concentration of 100 mg.L− 1, 150 mg.L− 1 were selected based on
OH− 108 effective dye removal efficiency and H2O2 concentration of 100 mg.L− 1
Fe2+ + HO2• ⎯⎯→ Fe3+ + (13) 0.72–1.5 was selected based on cost analysis (since dye removal efficiency nearly
HO2− × 106
the same for different H2O2 concentrations) in all dye concentration. The
Fe3+ + HO2• ⎯⎯→ Fe2+ + (14) 0.33–2.1
O 2 + H+ × 106 least-square method was followed to find out the best values of the ki­
•OH and HO2• radicals •OH + •OH ⎯⎯→ HO2• + (15) 5–8 × 109 netic parameters [65,66]. The sum of squared errors (SSE) was mini­
scavenging reaction OH− mized according to the methods for each specific dosage. Graphical
HO2• + HO2• ⎯⎯→ H2O2 (16) 0.8–2.2 comparison between the corresponding experimental results with the
+ O2 × 106
•OH + H2O2 ⎯⎯→ H2O + (17) 1.7–4.5
kinetic model has been utilized by finding out regression coefficient
HO2• × 107 values (goodness of model). Fig. 6 illustrates the plots of different kinetic
•OH + HO2• ⎯⎯→ H2O + (18) 1.4 × models and Table 3 shows the summarized results of regression co­
O2 1010 efficients (R2), rate constants (k), amount of dye absorbed (for
H2O2 decomposition 2H2O2 ⎯⎯→ 2H2O + O2 (19) –
pseudo-first and second-order). Comparing the regression coefficients
(absence of organic
pollutants) (R2), it can be depicted that, Fenton process follows the
Treatment Attacking C29H24N6 + •OH (20) – pseudo-second-order kinetic model (R2 values were very close to unity
of organic dye ⎯⎯→H2O + C29H23N6• in all cases). Apart from the pseudo-second-order model, the
organic (i.e. sudan (chain propagation) pseudo-first-order model and second-order model were also fitted better
dyes black B) C29H23N6• + H2O2 ⎯⎯→ (21)
C29H23N6OH + •OH
based on the goodness of fit data. R2 values of pseudo-first-order were
C29H23N6• + O2 ⎯⎯→ (22) between 0.75 and 0.91, where for second-order they were between 0.3
C29H23N6OO• and 0.97. Therefore, it can be depicted that degradation of SBB dye by
C29H23N6• + Fe3+ ⎯⎯→ (23) Fenton process follows pseudo-second-order kinetics model mostly. The
C29H23N6+ + Fe2+
rate constant at this model was varied from 0.0012 to 0.0036 g.mg− 1.
(oxidation)
C29H23N6• + Fe2+ ⎯⎯→ (24) min− 1 and the amount of dye adsorbed was in the range of 333–769 mg.
C29H23N6− + Fe3+ g− 1. Previous studies of Fenton-like processes and combined processes
(reduction) also justified the credibility of the pseudo-second-order kinetics model
2C29H23N6• ⎯⎯→ (25) in organic compounds degradation [16,52,67]. Experimental Qe
C29H23N6– C29H23N6
(dimerization)
(mgg− 1) for every case was very similar to calculated Qe in
Coagulants [Fe(H2O)6]3+ + H2O ↔ (26) pseudo-second-order kinetics which also proves the
Formation [Fe(H2O)5OH]2+ + pseudo-second-order to be the best-fitted model in dye degradation ki­
(complexes) H3O+ netics. Within 30 min treatment time, >90% of total degradation
[Fe(H2O)5OH]2+ + H2O (27)
occurred, which indicated the adsorption was dominated in the degra­
↔ [Fe(H2O)4(OH)2] +
H3O+ dation. Initially, availability of adsorbent was higher to adsorb SBB dye,
2[Fe(H2O)5OH]2+ ↔ [Fe (28) so does the rate of adsorption. Therefore, after scaling up the process
(H2O)8(OH)2]4+ + 2H2O additional power cost can be minimized by selecting optimum operating
[Fe(H2O)8(OH)2]4+ + (29) time. Moreover, the data demonstrated stronger pseudo-second order
H2O ↔
[Fe2(H2O)7(OH)3]3+ +
behavior. This may also imply the mechanism of removal is predomi­
H3O+ nantly adsorption as opposed to oxidation. Finally, all the kinetic pa­
[Fe2(H2O)7(OH)3]3+ (30) rameters have been determined for different models and placed in
+[Fe(H2O)5OH]2+ Table 3 for easy visualization and comparison among the model.
↔[Fe2(H2O)7(OH)4]5+
+2H2O
Adsorption C29H24N6 + Fe(OH)n(s) (31) 3.6. Complex organic dyes degradation mechanism
→ [Sludge](s)
Fenton’s reagent has different treatment functions depending on the
H2O2/Fe2+ ratio. When the amount of Fe2+ exceeds H2O2, the treatment
this condition was found at 1.86 $/kg of dye removal which is relatively process is dominated by chemical coagulation. In contrast, when the
better than Bilińska et al.(2016), ozone-based treatment operating cost amount of H2O2 exceeds Fe2+, the treatment process is dominated by
study. Though [64] didn’t consider per unit removal basis cost, the chemical oxidation [68]. Therefore, the optimum dosage of both Fe2+
operating costs were between 2.2 and 2.4 $/m3 for O3/UV, and H2O2 can create a balance on the rate of coagulation and oxidation
O3/UV/0.005 M H2O2, and O3/UV/0.01 M H2O2 treatment process. for better degradation purposes. Table 2 depicts the overall mechanism
Recently, combined processes have become very popular for higher of the Fenton process to degrade organic compounds. The principal re­
degradation capability along with lower sludge volume (e.g. action of the Fenton process is described in Eqn. 10, where H2O2 is
electrocoagulation-electrooxidation, advanced oxidation-membrane), catalyzed rapidly by Fe2+ to decompose into •OH that can oxidize the
but these processes are not cost effective. However, it has been found complex structure of the pollutants. This •OH has a strong oxidation
that the operating costs of the biological process combined with the capacity (standard potential = 2.80 V versus standard hydrogen elec­
Fenton process (Fenton process as a post-treatment) is quite low trode). Fe3+ is also generated from Eqn. 10 which further can be reduced
compared with other combined processes [41]. Thus, it can be suggested by H2O2 to produce Fe2+ and HO2• by the so-called Fenton-like reaction
that the optimum process condition found in the current study with the at a very slow rate (Eqn. 11). Both •OH and HO2• radicals can oxidize

6
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Fig. 4. Effect of initial Fe2+ concentration on color and dye removal keeping constant concentration of H2O2 (100 mgL− 1); a) and b) 50 mgL− 1 dye; c) and d) 70
mgL− 1 dye; e) and f) 100 mgL− 1 dye. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

Table 3
Kinetic parameters of Sudan black B dye degradation by Fenton process.
Dye;Fe2+; H2O2 50 mg.L− 1;150 50 mg.L− 1; 100 70 mg.L− 1; 150 70 mg.L− 1; 100 100 mg.L− 1; 150 100 mg.L− 1; 100
mg.L− 1; 100 mg. mg.L− 1; 100 mg. mg.L− 1; 100 mg. mg.L− 1; 100 mg. mg.L− 1; 100 mg. mg.L− 1; 100 mg.
L− 1 L− 1 L− 1 L− 1 L− 1 L− 1

Kinetic Zero order k0 (mg.L− 1. 1.0672 0.9757 1.4157 1.2216 1.9521 1.6971
parameter min− 1)
R2 0.2294 0.2669 0.2419 0.1960 0.2085 0.2186
First order k1 (min− 1) 0.0730 0.0471 0.0541 0.0342 0.0469 0.0321
R2 0.5643 0.4800 0.4552 0.2357 0.3058 0.2813
Second k2 (mg− 1.L. 0.0120 0.0033 0.0034 0.0012 0.0016 0.0007
order min− 1)
R2 0.9706 0.7889 0.7949 0.3004 0.4253 0.3791
Pseudo first k3 (min− 1) 0.0711 0.0737 0.0694 0.0821 0.0571 0.0655
order Qe (mg.g− 1) 133.22 235.36 190.80 172.47 290.41 201.04
calc.
Qe (mg.g− 1) 326.94 451.36 435.76 555.25 597.41 787.67
exp.
R2 0.8464 0.9113 0.8607 0.8096 0.7455 0.7639
Pseudo k4 (g.mg− 1. 0.0027 0.0012 0.0018 0.0036 0.0022 0.0014
second min− 1)
order Qe (mg.g− 1) 333.33 454.55 434.78 555.56 588.24 769.23
R2 0.9999 0.9997 0.9999 1.000 0.9999 0.9999

the organic compounds of dye but HO2• is less sensitive than •OH for reactions. A few researchers proposed some radical–radical reactions or
that purpose. Eqn. 11 further initialize the Eqn. 10 and both of these H2O2–radical reactions may occur, which have very high reaction rate
reactions mainly summarize the overall Fenton process (Fischbacher constants (Eqn. 15–18). The decomposition of H2O2 also occurs in the
et al., 2017; [41]. absence of organic compounds (Eqn. 19). Though the main target of the
Researchers also considered some other steps to happen during the Fenton reaction is to generate •OH, it can be scavenged by various re­
main reactions. Eqn. 12–14 are reported rate-determining steps since actions i.e., Fe2+ (Eqn. 12), H2O2 (Eqn. 17), HO2• (Eqn. 18), and/or even
H2O2 is consumed and Fe2+ is regenerated from Fe3+ through these auto scavenged (Eqn. 15) [30,69].

7
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

Fig. 5. Effect of initial SBB dye concentration on color and dye removal. (For interpretation of the references to color in this figure legend, the reader is referred to
the Web version of this article.)

Fig. 6. SBB dye degradation kinetics using zero-order, first order, second order, pseudo-first-order and pseudo-second-order kinetic models.

•OH can oxidize organic dyes i.e SBB (C29H24N6) and produce highly by reacting with available H2O2 in the solution following Eqn. 21.
reactive free radicals (C29H23N6•) (Eqn. 20). This is the chain propa­ However, C29H23N6• may be oxidized by Fe3+, reduced by Fe2+, or
gation step of attacking organic dyes. C29H23N6• can also generate •OH dimerized later by following Eqn. 23–25. The generated Fe2+ in the

8
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

oxidation reaction (Eqn. 23) competes with the generation of •OH (Eqn. communications with the office). He is responsible for communicating
10) and consumption of •OH (Eqn. 20). So, •OH can be produced with the other authors about progress, submissions of revisions and final
indirectly by the organic radicals present in the wastewater (Eqn. 10, approval of proofs. We confirm that we have provided a current, correct
Eqn. 23) and can degrade organic molecules to produce organic radicals email address which is accessible by the Corresponding Author.
further to continue chain reactions of Fenton chemistry (Eqn. 20) [30, [73–100].
70]; Shuchi et al., 2020). Meanwhile, Fe2+ reacts with hydroxide ions to
form ferric hydroxo complexes (Eqn. 26–27). Eqn. 26–30 represents the Declaration of competing interest
complex (Fenton reagent) formation and further steps (Eqn. 28–30,
when pH ranges between 3 and 7) that contribute to the coagulation The authors declare that they have no known competing financial
capability of the Fenton process. Dissolved suspended solids are then interests or personal relationships that could have appeared to influence
captured and precipitated by the above Fenton reagents but small flocs the work reported in this paper.
are observed continually that takes a very long time, sometimes over­
night for the settlement. Daneshvar et al. (2006) proposed that the flocs Acknowledgments
further adsorbed by Fe(OH)n with the surface complexation method and
removed from the process (Eqn. 31). Chemical coagulation using poly­ We acknowledge Bangladesh University of Engineering and Tech­
mer is also necessary for further treatment [71,72]. Kinetic analysis of nology (BUET) for contributing financial support for the project and
this study in Section 3.5 also followed this adsorption mechanism where Department of Chemical Engineering, BUET, to provide lab facilities for
degradation data fits quite accurately to the pseudo-second-order kinetic conducting experiments and sample analysis.
model.
Competition for hydroxyl radicals among Fe2+, C29H24N6, and Fe3+ References
results in non-useful hydrogen peroxide decomposition and reduces the
yield of hydroxylated (oxidized) organic compounds (Eqn. 19). There­ [1] M.R. Al-Mamun, M.S. Islam, M.R. Hossain, S. Kader, M.S. Islam, M.Z.H. Khan,
A novel and highly efficient Ag and GO co-synthesized ZnO nano photocatalyst
fore, to maximize the efficiency of the degradation process stoichio­
for methylene blue dye degradation under UV irradiation, Environ. Nanotechnol.
metric relationships among them need to be established. An adequate Monitoring Manag. 16 (2021) 100495, https://doi.org/10.1016/j.
amount of reactants can be a viable alternative to degrade the organic enmm.2021.100495.
[2] M.R. Al-Mamun, S. Kader, M.S. Islam, M.Z.H. Khan, Photocatalytic activity
compounds completely to CO2 and water by experimenting for suitable
improvement and application of UV-TiO2 photocatalysis in textile wastewater
reaction time [68,69,72]. treatment: a review, J. Environ. Chem. Eng. (2019), https://doi.org/10.1016/j.
jece.2019.103248.
4. Conclusion [3] M.B.K. Suhan, S.B. Shuchi, A. Anis, Z. Haque, M.S. Islam, Comparative degra­
dation study of remazol black B dye using electro-coagulation and electro-Fenton
process: kinetics and cost analysis, Environ. Nanotechnol. Monit. Manag. 14
The Fenton process removed dye effectively, however, the dye (2020) 100335, https://doi.org/10.1016/j.enmm.2020.100335.
removal was decreased with the increase of dye concentration for a [4] H. Hassan, B.H. Hameed, Fenton-like oxidation of acid Red 1 solutions using
heterogeneous catalyst based on ball clay, Int. J. Environ. Sci. Te. 2 (3) (2011)
particular dose of Fe2+ and H2O2. The optimum Fe2+ and H2O2 doses 218–222, https://doi.org/10.7763/ijesd.2011.v2.127.
were 150 mg.L− 1 and 100 mg.L− 1, respectively. At the optimum con­ [5] M.J. Wesley, R.N. Lerner, E.S. Kim, M.S. Islam, Y. Liu, Biological fixed film, Water
dition, 95% and 85% of dye and color were removed, respectively, Environ. Res. 83 (2011) 1150–1186, https://doi.org/10.2175/
106143011X13075599869254.
within 30 min of experimental time for the treatment of 50 mg.L− 1 dye. [6] K. Rambabu, A. Thanigaivelan, G. Bharath, N. Sivarajasekar, F. Banat, P.L. Show,
Dye degradation followed the first-order kinetics for all experimental Biosorption potential of Phoenix dactylifera coir wastes for toxic hexavalent
conditions. Cost analysis showed the Fenton process as a promising and chromium sequestration, Chemosphere (2020) 128809, https://doi.org/
10.1016/j.chemosphere.2020.128809.
cost-effective method to apply industrially. Besides, the Fenton process [7] K. Rambabu, G. Bharath, A. Thanigaivelan, D.B. Das, P.L. Show, F. Banat,
is a non-toxic (H2O2 breaks down to H2O and O2), simple, easy (oper­ Augmented biohydrogen production from rice mill wastewater through nano-
ation at room temperature and atmospheric pressure) and environ­ metal oxides assisted dark fermentation, Bioresour. Technol. 319 (2021) 124243,
https://doi.org/10.1016/j.biortech.2020.124243.
mentally friendly method to degrade organics from wastewater.
[8] P. Pourrezaei, A. Afzal, N. Ding, M.S. Islam, A. Moustafa, P. ł A. Drzewicz, M.
Effectiveness application of Fenton process treating textile wastewater G. El-Din, Physico-chemical processes, Water Environ. Res. 82 (10) (2010)
largely depends on selection of it as an intermediate or final treatment 997–1072, https://doi.org/10.2175/106143010x12756668800852.
based on the effluent standard discharge criteria and economic viability. [9] F.M. Mohamed, K.A. Alfalous, The effectiveness of activated silica derived from
rice husk in coagulation process compared with inorganic coagulants for waste­
Therefore, this study will bridge the gap between economy and effective water treatment, Egypt, J. Aquat. Res. 46 (2) (2020) 131–136, https://doi.org/
degradation of effluents with respect to SBB dye treatment by Fenton 10.1016/j.ejar.2020.03.004.
oxidation process. [10] K. Rambabu, G. Bharath, P. Monash, S. Velu, F. Banat, M. Naushad,
G. Arthanareeswaran, P.L. Show, Effective treatment of dye polluted wastewater
using nanoporous CaCl2 modified polyethersulfone membrane, Process Saf. En­
Authors declaration viron. 124 (2019) 266–278, https://doi.org/10.1016/j.psep.2019.02.015.
[11] F. Ali, N. Ali, I. Bibi, A. Said, S. Nawaz, Z. Ali, S.M. Salman, H.M.N. Iqbal, M. Bilal,
Adsorption isotherm, kinetics and thermodynamic of Acid blue and Basic blue
We wish to confirm that there are no known conflicts of interest dyes onto activated charcoal, Case Studies in Chemical and Environmental En­
associated with this publication and there has been no significant gineering 100040 (2020), https://doi.org/10.1016/j.cscee.2020.100040.
financial support for this work that could have influenced its outcome. [12] K. Rambabu, J. AlYammahi, G. Bharath, A. Thanigaivelan, N. Sivarajasekar,
F. Banat, Nano-activated carbon derived from date palm coir waste for efficient
We confirm that the manuscript has been read and approved by all sequestration of noxious 2, 4-dichlorophenoxyacetic acid herbicide, Chemosphere
named authors and that there are no other persons who satisfied the 131103 (2021), https://doi.org/10.1016/j.chemosphere.2021.131103.
criteria for authorship but are not listed. We further confirm that the [13] M. Hasan Khan Neon, M.S. Islam, MoO3 and Ag co-synthesized TiO2 as a novel
heterogeneous photocatalyst with enhanced visible-light-driven photocatalytic
order of authors listed in the manuscript has been approved by all of us. activity for methyl orange dye degradation, Environ. Nanotechnol. Monitoring
We confirm that we have given due consideration to the protection of Manag. 12 (2019) 100244, https://doi.org/10.1016/j.enmm.2019.100244.
intellectual property associated with this work and that there are no [14] M.R. Al-Mamun, M.S. Islam, M.R. Hossain, S. Kader, M.S. Islam, M.Z.H. Khan,
A novel and highly efficient Ag and GO co-synthesized ZnO nano photocatalyst
impediments to publication, including the timing of publication, with
for methylene blue dye degradation under UV irradiation, Environ. Nanotechnol.
respect to intellectual property. In so doing we confirm that we have Monitoring Manag. 16 (2021) 100495, https://doi.org/10.1016/j.
followed the regulations of our institutions concerning intellectual enmm.2021.100495.
property. [15] M.S. Islam, Y. Zhang, K.N. McPhedran, Y. Liu, M.G. El-Din, Analysis of microbial
biofilm communities developed on granular activated carbon in oil sands process-
We understand that the Corresponding Author is the sole contact for affected water treatment using next-generation pyrosequencing, Appl. Environ.
the Editorial process (including Editorial Manager and direct Microbiol. (2015), https://doi.org/10.1128/AEM.04258-14.

9
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

[16] Z. Al-Qodah, M. Tawalbeh, M. Al-Shannag, Z. Al-Anber, K. Bani-Melhem, Com­ [39] J.P. Kushwaha, V.C. Srivastava, I.D. Mall, Organics removal from dairy waste­
bined electrocoagulation processes as a novel approach for enhanced pollutants water by electrochemical treatment and residue disposal, Separ. Purif. Technol.
removal: a state-of-the-art review, Sci. Total Environ. 744 (2020) 140806, 76 (2) (2010) 198–205, https://doi.org/10.1016/j.seppur.2010.10.008.
https://doi.org/10.1016/j.scitotenv.2020.140806. [40] E. Mohora, S. Rončević, J. Agbaba, A. Tubić, M. Mitić, M. Klašnja, B. Dalmacija,
[17] M.R. Al-Mamun, M.N. Karim, N. Afroj, S. Kader, M.S. Islam, M.Z.H. Khan, Pho­ Removal of arsenic from groundwater rich in natural organic matter (NOM) by
tocatalytic performance assessment of GO and Ag co-synthesized TiO2 nano­ continuous electrocoagulation/flocculation (ECF), Separ. Purif. Technol. 136
composite for the removal of methyl orange dye under solar irradiation, Environ. (2014) 150–156, https://doi.org/10.1016/j.seppur.2014.09.006.
Technol. Innov. 101537 (2021), https://doi.org/10.1016/j.eti.2021.101537. [41] M. Xu, C. Wu, Y. Zhou, Advancements in the fenton process for wastewater
[18] M.S. Islam, T. Dong, K.N. McPhedran, Z. Sheng, Y. Zhang, Y. Liu, M.G. El-Din, treatment. Advanced Oxidation Processes - Applications, Trends, and Prospects
Impact of ozonation pre-treatment of oil sands process-affected water on the (2020), https://doi.org/10.5772/intechopen.90256.
operational performance of a GAC-fluidized bed biofilm reactor, Biodegradation [42] D.A. Yaseen, M. Scholz, Treatment of synthetic textile wastewater containing dye
25 (6) (2014) 811–823, https://doi.org/10.1007/s10532-014-9701-6. mixtures with microcosms, Environ. Sci. Pollut. Res. 25 (2) (2018) 1980–1997,
[19] A. Kiran, M. Ramzan, M. Faheem, S. Hussain, M. Imran, Catalytic degradation of https://doi.org/10.1007/s11356-017-0633-7.
methylene blue using a newly engineered composite and its electrochemical [43] L. Guo, F. Chen, X. Fan, W. Cai, J. Zhang, S-doped α-Fe2O3 as a highly active
performance, Case Studies in Chemical and Environmental Engineering 2 (2020) heterogeneous Fenton-like catalyst towards the degradation of acid orange 7 and
100039, https://doi.org/10.1016/j.cscee.2020.100039. phenol, Appl. Catal. B Environ. 96 (1–2) (2010) 162–168, https://doi.org/
[20] D. Cecconet, D. Molognoni, A. Callegari, A.G. Capodaglio, Biological combination 10.1016/j.apcatb.2010.02.015.
processes for efficient removal of pharmaceutically active compounds from [44] S.L. Stupar, B.N. Grgur, M.M. Radišić, A.E. Onjia, N.D. Ivanković, A.V. Tomašević,
wastewater: a review and future perspectives, J. Environ. Chem. Eng. 5 (4) (2017) D. Mijin, Oxidative degradation of acid blue 111 by electro-assisted fenton pro­
3590–3603, https://doi.org/10.1016/j.jece.2017.07.020. cess, J. Water Process Eng. 36 (2020), https://doi.org/10.1016/j.
[21] B. Tiwari, B. Sellamuthu, Y. Ouarda, P. Drogui, R.D. Tyagi, G. Buelna, Review on jwpe.2020.101394. November 2019.
fate and mechanism of removal of pharmaceutical pollutants from wastewater [45] S. Wang, J.H. Kwak, M.S. Islam, M.A. Naeth, M.G. El-Din, S.X. Chang, Biochar
using biological approach, Biores. Technol. 224 (2017) 1–12, https://doi.org/ surface complexation and Ni (II), Cu (II), and Cd (II) adsorption in aqueous so­
10.1016/j.biortech.2016.11.042. lutions depend on feedstock type, Sci. Total Environ. 712 (2020) 136538, https://
[22] F.D. Chequer, G.R. De Oliveira, E.A. Ferraz, J.C. Cardoso, M.B. Zanoni, D.P. de doi.org/10.1016/j.scitotenv.2020.136538.
Oliveira, Textile dyes: dyeing process and environmental impact, Eco-friendly [46] E.K. Maher, K.N. O’Malley, J. Heffron, J. Huo, B.K. Mayer, Y. Wang, P.
Textile Dyeing Finishing 6 (6) (2013) 151–176, https://doi.org/10.5772/53659. J. McNamara, Analysis of operational parameters, reactor kinetics, and floc
[23] Z. Al-Qodah, M. Al-Shannag, K. Bani-Melhem, E. Assirey, M.A. Yahya, A. Al- characterization for the removal of estrogens via electrocoagulation, Chemo­
Shawabkeh, Free radical-assisted electrocoagulation processes for wastewater sphere 220 (2019) 1141–1149.
treatment, Environ. Chem. Lett. 16 (2018) 695–714, https://doi.org/10.1007/ [47] M.S. Islam, J.-H. Kwak, C. Nzediegwu, S. Wang, K. Palansuriya, E.E. Kwon,
s10311-018-0711-1. M. AnneNaeth, M. Gamal El-Din, Y.S. Ok, S.X. Chang, Biochar heavy metal
[24] K. Rambabu, G. Bharath, A. Hai, S. Luo, K. Liao, M.A. Haijaa, M. Naushad, removal in aqueous solution depends on feedstock type and pyrolysis purging gas,
Development of watermelon rind derived activated carbon/manganese ferrite Environ. Pollut. 281 (2021) 117094, https://doi.org/10.1016/j.
nanocomposite for cleaner desalination by capacitive deionization, J. Clean. envpol.2021.117094.
Prod. 122626 (2020), https://doi.org/10.1016/j.jclepro.2020.122626. [48] Z. Berk, Chapter 7 – mixing, Food Process Engineering and Technology 175
[25] F. Duarte, F.J. Maldonado-Hódar, L.M. Madeira, Influence of the characteristics of (2009), https://doi.org/10.1016/B978-0-12-373660-4.00007-7.
carbon materials on their behaviour as heterogeneous Fenton catalysts for the [49] E. Basturk, M. Karatas, Advanced oxidation of reactive blue 181 solution: a
elimination of the azo dye Orange II from aqueous solutions, Appl. Catal. B En­ comparison between Fenton and sono-Fenton process, Ultrason. Sonochem. 21
viron. 103 (1–2) (2011) 109–115, https://doi.org/10.1016/j. (5) (2014) 1881–1885, https://doi.org/10.1016/j.ultsonch.2014.03.026.
apcatb.2011.01.016. [50] I. Mesquita, L.C. Matos, F. Duarte, F.J. Maldonado-hódar, A. Mendes, L.
[26] N. Wang, T. Zheng, G. Zhang, P. Wang, A review on Fenton-like processes for M. Madeira, Treatment of azo dye-containing wastewater by a Fenton-like process
organic wastewater treatment, J. Environ. Chem. Eng. 4 (1) (2016) 762–787, in a continuous packed-bed reactor filled with activated carbon, J. Hazard Mater.
https://doi.org/10.1016/j.jece.2015.12.016. 237–238 (2012) 30–37, https://doi.org/10.1016/j.jhazmat.2012.07.066.
[27] J.J. Pignatello, E. Oliveros, A. MacKay, Advanced oxidation processes for organic [51] B. Li, Y. Dong, C. Zou, Y. Xu, Iron(III)-alginate fiber complex as a highly effective
contaminant destruction based on the fenton reaction and related chemistry, Crit. and stable heterogeneous fenton photocatalyst for mineralization of organic dye,
Rev. Environ. Sci. Technol. 36 (1) (2006) 1–84, https://doi.org/10.1080/ Ind. Eng. Chem. Res. 53 (11) (2014) 4199–4206, https://doi.org/10.1021/
10643380500326564. ie404241r.
[28] M.H. Zhang, H. Dong, L. Zhao, D.X. Wang, D. Meng, A review on Fenton process [52] S. Hashemian, Fenton-like oxidation of malachite green solutions: kinetic and
for organic wastewater treatment based on optimization perspective, Sci. Total thermodynamic study, J. Chem. (2013), https://doi.org/10.1155/2013/809318.
Environ. 670 (2019) 110–121, https://doi.org/10.1016/j.scitotenv.2019.03.180. [53] P.J.D. Ranjit, K. Palanivelu, C.S. Lee, Degradation of 2, 4-dichlorophenol in
[29] P. Marcus, V. Maurice, Investigations of structure and stability of passive films by aqueous solution by sono-Fenton method, Korean J. Chem. Eng. 25 (1) (2008)
surface analytical techniques, Encyclopedia Interfac. Chem. (2018) 259–266, 112–117, https://doi.org/10.1007/s11814-008-0020-7.
https://doi.org/10.1016/B978-0-12-409547-2.13818-1. [54] L. Gomathi Devi, S. Girish Kumar, K. Mohan Reddy, C. Munikrishnappa, Photo
[30] A. Babuponnusami, K. Muthukumar, A review on Fenton and improvements to degradation of methyl orange an azo dye by advanced Fenton process using zero
the Fenton process for wastewater treatment, J. Environ. Chem. Eng. 2 (1) (2014) valent metallic iron: influence of various reaction parameters and its degradation
557–572, https://doi.org/10.1016/j.jece.2013.10.011. mechanism, J. Hazard Mater. 164 (2–3) (2009) 459–467.
[31] S. Yuan, N. Gou, A.N. Alshawabkeh, A.Z. Gu, Efficient degradation of contami­ [55] R. Biondi, S. Brancorsini, G. Poli, M.G. Egidi, E. Capodicasa, L. Bottiglieri, S. Gerli,
nants of emerging concerns by a new electro-Fenton process with Ti/MMO E. Brillo, G.C.D. Renzo, D. Cretoiu, Detection and scavenging of hydroxyl radical
cathode, Chemosphere 93 (11) (2013) 2796–2804, https://doi.org/10.1016/j. via D-phenylalanine hydroxylation in human fluids, Talanta 181 (2018) 172–181,
chemosphere.2013.09.051. https://doi.org/10.1016/j.talanta.2017.12.084.
[32] B. Lellis, C.Z. Fávaro-Polonio, J.A. Pamphile, J.C. Polonio, Effects of textile dyes [56] L.G. Devi, S.G. Kumar, K.M. Reddy, C. Munikrishnappa, Photo degradation of
on health and the environment and bioremediation potential of living organisms, Methyl Orange an azo dye by Advanced Fenton Process using zero valent metallic
Biotechnol. Res. Innov. 3 (2) (2019) 275–290, https://doi.org/10.1016/j. iron: influence of various reaction parameters and its degradation mechanism,
biori.2019.09.001. J. Hazard Mater. 164 (2–3) (2009) 459–467, https://doi.org/10.1016/j.
[33] E. Safaralizadeh, S.J. Darzi, A.R. Mahjoub, R. Abazari, Visible light-induced jhazmat.2008.08.017.
degradation of phenolic compounds by Sudan black dye sensitized TiO 2 nano­ [57] F.J. Rivas, F.J. Beltran, J. Frades, P. Buxeda, Oxidation of p-hydroxybenzoic acid
particles as an advanced photocatalytic material, Res Chem. Intermediat. 43 (2) by Fenton’s reagent, Water Res. 35 (2) (2001) 387–396, https://doi.org/
(2017) 1197–1209, https://doi.org/10.1007/s11164-016-2692-7. 10.1016/S0043-1354(00)00285-2.
[34] J. Fu, T. Chen, H. Lu, Y. Lin, X. Xie, H. Tian, C. Zheng, D. He, Enhancement of [58] F.J. Benitez, J.L. Acero, F.J. Real, F.J. Rubio, A.I. Leal, The role of hydroxyl
docosahexaenoic acid production by low-energy ion implantation coupled with radicals for the decomposition of p-hydroxy phenylacetic acid in aqueous solu­
screening method based on Sudan black B staining in Schizochytrium sp, Biores. tions, Water Res. 35 (5) (2001) 1338–1343, https://doi.org/10.1016/S0043-
Technol. 221 (2016) 405–411, https://doi.org/10.1016/j.biortech.2016.09.058. 1354(00)00364-X.
[35] C. Jiang, S. Pang, F. Ouyang, J. Ma, J. Jiang, A new insight into Fenton and [59] C.V. Rao, A.S. Giri, V.V. Goud, Studies on pH-dependent color variation and
Fenton-like processes for water treatment, J. Hazard Mater. 174 (1–3) (2010) decomposition mechanism of Brilliant Green dye in Fenton reaction, Int. J. Ind.
813–817, https://doi.org/10.1016/j.jhazmat.2009.09.125. Chem. 7 (2016) 71–80, https://doi.org/10.1007/s40090-015-0060-x.
[36] H. Guo, Z. Li, Y. Zhang, N. Jiang, H. Wang, J. Li, Degradation of chloramphenicol [60] S. Foteinis, J.M. Monteagudo, A. Durán, E. Chatzisymeon, Environmental sus­
by pulsed discharge plasma with heterogeneous Fenton process using Fe3O4 tainability of the solar photo-Fenton process for wastewater treatment and
nanocomposites, Separ. Purif. Technol. 117540 (2020). pharmaceuticals mineralization at semi-industrial scale, Sci. Total Environ. 612
[37] S.C. Azimi, F. Shirini, A. Pendashteh, Treatment of wood industry wastewater by (2018) 605–612, https://doi.org/10.1016/j.scitotenv.2017.08.277.
combined coagulation-flocculation-decantation and fenton process, Water Envi­ [61] S.K. Patel, S.G. Patel, G.V. Patel, Degradation of reactive dye in aqueous solution
ron. Res. (2020), https://doi.org/10.1002/wer.1441. by fenton, photo-fenton process and combination process with activated charcoal
[38] B. Jain, A. Hashmi, S. Sanwaria, A.K. Singh, M.A.B.H. Susan, A. Singh, Zinc oxide and TiO2, Proc. Natl. Acad. Sci., India, Sect. A Phys. Sci. 90 (2020) 579–591,
nanoparticle incorporated on graphene oxide: an efficient and stable photo­ https://doi.org/10.1007/s40010-019-00618-3.
catalyst for water treatment through the Fenton process, Adv. Comp. Hybrid [62] C. Sirtori, A. Zapata, I. Oller, W. Gernjak, A. Agüera, S. Malato, Decontamination
Mater. (2020), https://doi.org/10.1007/s42114-020-00153-5. industrial pharmaceutical wastewater by combining solar photo-Fenton and

10
M.B.K. Suhan et al. Case Studies in Chemical and Environmental Engineering 4 (2021) 100126

biological treatment, Water Res. 43 (3) (2009) 661–668, https://doi.org/ tartrazine, Food Chem. Toxicol. 48 (10) (2010) 2934–2944, https://doi.org/
10.1016/j.watres.2008.11.013. 10.1016/j.fct.2010.07.030.
[63] J. Blanco, F. Torrades, M.D. Varga, J. García-Montaño, Fenton and biological- [85] R. Muthezhilan, N. Yogananth, S. Vidhya, S. Jayalakshmi, Dye degrading myco­
Fenton coupled processes for textile wastewater treatment and reuse, Desalina­ flora from industrial effluents, Res. J. Microbiol. 3 (3) (2008) 204–208.
tion 286 (2012) 394–399, https://doi.org/10.1016/j.desal.2011.11.055. [86] M.H.K. Neon, M.S. Islam, MoO3 and Ag co-synthesized TiO2 as a novel hetero­
[64] L. Bilińska, M. Gmurek, S. Ledakowicz, Comparison between industrial and geneous photocatalyst with enhanced visible-light-driven photocatalytic activity
simulated textile wastewater treatment by AOPs – biodegradability, toxicity and for Methyl Orange dye degradation, Environ. Nanotechnol. Monit. Manag. 12
cost assessment, Chem. Eng. J. 306 (2016) 550–559, https://doi.org/10.1016/j. (2019) 100244, https://doi.org/10.1016/j.enmm.2019.100244.
cej.2016.07.100. [87] B. Neppolian, J.S. Park, H. Choi, Effect of Fenton-like oxidation on enhanced
[65] C. Gerald, P. Wheatley, Applied Numerical Analysis, seventh ed., Addison and oxidative degradation of para-chlorobenzoic acid by ultrasonic irradiation,
Wesley, 2004. Ultrason. Sonochem. 11 (5) (2004) 273–279, https://doi.org/10.1016/j.
[66] M. Al-Shannag, Z. Al-Qodah, K. Bani-Melhem, M.R. Qtaishat, M. Alkasrawi, ultsonch.2003.11.001.
Heavy metal ions removal from metal plating wastewater using electro­ [88] P.V. Nidheesh, R. Gandhimathi, Trends in electro-Fenton process for water and
coagulation: kinetic study and process performance, Chem. Eng. J. 260 (2015) wastewater treatment: an overview, Desalination 299 (2012) 1–15, https://doi.
749–756, https://doi.org/10.1016/j.cej.2014.09.035. org/10.1016/j.desal.2012.05.011.
[67] A.O. Ifelebuegu, C.P. Ezenwa, Removal of endocrine disrupting chemicals in [89] M.I. Pariente, J.A. Siles, R. Molina, J.A. Botas, J.A. Melero, F. Martinez, Treat­
wastewater treatment by fenton-like oxidation, Water Air Soil Pollut. 217 (1–4) ment of an agrochemical wastewater by integration of heterogeneous catalytic
(2011) 213–220, https://doi.org/10.1007/s11270-010-0580-0. wet hydrogen peroxide oxidation and rotating biological contactors, Chem. Eng.
[68] E. Neyens, J. Baeyens, A review of classic Fenton’s peroxidation as an advanced J. (2013), https://doi.org/10.1016/j.cej.2013.04.081, 226, 409-415.
oxidation technique, J. Hazard Mater. 98 (1–3) (2003) 33–50, https://doi.org/ [90] S. Pilli, B. Sellamuthu, A.K. Pandey, R.D. Tyagi, Treatment of wastewater con­
10.1016/S0304-3894(02)00282-0. taining pharmaceuticals: biological treatment, Current Developments in
[69] A.D. Bokare, W. Choi, Review of iron-free Fenton-like systems for activating H2O2 Biotechnology and Bioengineering (2020) 463–520, https://doi.org/10.1016/
in advanced oxidation processes, J. Hazard Mater. 275 (2014) 121–135, https:// b978-0-12-819722-6.00013-4.
doi.org/10.1016/j.jhazmat.2014.04.054. [91] K. Rambabu, S. Velu, Modified polyethersulfone ultrafiltration membrane for the
[70] Y. Zhang, M. Zhou, A critical review of the application of chelating agents to treatment of tannery wastewater, Int. J. Environ. Stud. 73 (5) (2016) 819–826,
enable Fenton and Fenton-like reactions at high pH values, J. Hazard Mater. 362 https://doi.org/10.1080/00207233.2016.1153900.
(2019) 436–450, https://doi.org/10.1016/j.jhazmat.2018.09.035. [92] O. Sahu, Electro-oxidation and chemical oxidation treatment of sugar industry
[71] N. Daneshvar, A. Oladegaragoze, N. Djafarzadeh, Decolorization of basic dye wastewater with ferrous material: an investigation of physicochemical charac­
solutions by electrocoagulation: an investigation of the effect of operational pa­ teristic of sludge, S. Afr. J. Chem. Eng. 28 (2019) 26–38, https://doi.org/
rameters, J. Hazard Mater. 129 (1–3) (2006) 116–122, https://doi.org/10.1016/ 10.1016/j.sajce.2019.01.004.
j.jhazmat.2005.08.033. [93] S.P. Sun, C.J. Li, J.H. Sun, S.H. Shi, M.H. Fan, Q. Zhou, Decolorization of an azo
[72] Q.Q. Cai, L. Jothinathan, S.H. Deng, S.L. Ong, H.Y. Ng, J.Y. Hu, Fenton- and dye Orange G in aqueous solution by Fenton oxidation process: effect of system
ozone-based AOP processes for industrial effluent treatment. Advanced Oxidation parameters and kinetic study, J. Hazard Mater. 161 (2–3) (2009) 1052–1057,
Processes for Effluent Treatment Plants, 2021, pp. 199–254, https://doi.org/ https://doi.org/10.1016/j.jhazmat.2008.04.080.
10.1016/b978-0-12-821011-6.00011-6. [94] H. Xu, T.M. Heinze, S. Chen, C.E. Cerniglia, H. Chen, Anaerobic metabolism of 1-
[73] W.C. Bray, The interaction of ozone and hydrogen peroxide in aqueous solution, amino-2-naphthol-based azo dyes (Sudan dyes) by human intestinal microflora,
J. Am. Chem. Soc. 60 (1) (1938) 82–87, https://doi.org/10.1021/ja01268a027. Appl. Environ. Microbiol. 73 (23) (2007) 7759–7762, https://doi.org/10.1128/
[74] J.S. Chang, C. Chou, Y.C. Lin, P.J. Lin, J.Y. Ho, T. Lee Hu, Kinetic characteristics aem.01410-07.
of bacterial azo-dye decolorization by Pseudomonas luteola, Water Res. 35 (12) [95] H. Xu, T.M. Heinze, D.D. Paine, C.E. Cerniglia, H. Chen, Sudan azo dyes and para
(2001) 2841–2850, https://doi.org/10.1016/S0043-1354(00)00581-9. red degradation by prevalent bacteria of the human gastrointestinal tract,
[75] A. Downham, P. Collins, Colouring our foods in the last and next millennium, Int. Anaerobe 16 (2) (2010) 114–119, https://doi.org/10.1016/j.
J. Food Sci. Technol. 35 (1) (2000) 5–22, https://doi.org/10.1046/j.1365- anaerobe.2009.06.007.
2621.2000.00373.x. [96] X.R. Xu, H.B. Li, W.H. Wang, J.D. Gu, Degradation of dyes in aqueous solutions by
[76] H.J.H. Fenton, Oxidation of tartatic acid in presence of iron, J. Chem. Soc. Trans. the Fenton process, Chemosphere 57 (7) (2004) 595–600, https://doi.org/
65 (1894) 899–910. 10.1016/j.chemosphere.2004.07.030.
[77] A. Fischbacher, C. von Sonntag, T.C. Schmidt, Hydroxyl radical yields in the [97] M.S. Yalfani, S. Contreras, F. Medina, J. Sueiras, Phenol degradation by Fenton’s
Fenton process under various pH, ligand concentrations and hydrogen peroxide/ process using catalytic in situ generated hydrogen peroxide, Appl. Catal. B En­
Fe(II) ratios, Chemosphere 182 (2017) 738–744, https://doi.org/10.1016/j. viron. 89 (3–4) (2009) 519–526, https://doi.org/10.1016/j.apcatb.2009.01.007.
chemosphere.2017.05.039. [98] W.M.K. Zahid, Tertiary filtration of wastewater using local sand, J. King Saud
[78] F. Haber, J. Weiss, The catalytic decomposition of hydrogen peroxide by iron Univ. Eng. Sci. 16 (1) (2003) 23–35, https://doi.org/10.1016/s1018-3639(18)
salts, Proc. Roy. Soc. Lond. A. 147 (861) (1934) 332–351, https://doi.org/ 30778-5.
10.1098/rspa.1934.0221. [99] X. Zhao, I.R. Hardin, HPLC and spectrophotometric analysis of biodegradation of
[79] S. Kumar, S. Raut, P. Bandyopadhyay, Fungal decolouration and degradation of azo dyes by Pleurotus ostreatus, Dyes Pigments 73 (3) (2007) 322–325, https://
azo dyes : a review, Fungal Biol. Rev. (2016), https://doi.org/10.1016/j. doi.org/10.1016/j.dyepig.2005.11.014.
fbr.2016.06.003. [100] S.B. Shuchi, M.B.K. Suhan, S.B. Humayun, M.E. Haque, M.S. Islam, Heat-activated
[80] W.K. Lafi, Z. Al-Qodah, Combined advanced oxidation and biological treatment potassium persulfate treatment of Sudan Black B dye: degradation kinetic and
processes for the removal of pesticides from aqueous solutions, J. Hazard Mater. thermodynamic studies, J. Water Process. Eng. (2021), https://doi.org/10.1016/
137 (1) (2006) 489–497, https://doi.org/10.1016/j.jhazmat.2006.02.027. j.jwpe.2020.101690.
[81] S.H. Lin, C.C. Lo, Fenton process for treatment of desizing wastewater, Water Res.
31 (8) (1997) 2050–2056, https://doi.org/10.1016/S0043-1354(97)00024-9.
[82] R. Liu, H.M. Chiu, C.S. Shiau, R.Y.L. Yeh, Y.T. Hung, Degradation and sludge Md Burhan Kabir Suhan, S.M. Tanveer Mahtab, Wafi Aziz, Sonia Akter,
production of textile dyes by Fenton and photo-Fenton processes, Dyes Pigments Md Shahinoor Islam*
73 (1) (2007) 1–6, https://doi.org/10.1016/j.dyepig.2005.10.002. Department of Chemical Engineering, Bangladesh University of Engineering
[83] M.S. Lucas, J.A. Peres, Decolorization of the azo dye reactive black 5 by Fenton
and photo-Fenton oxidation, Dyes Pigments 71 (3) (2006) 236–244, https://doi.
and Technology, Dhaka, 1000, Bangladesh
org/10.1016/j.dyepig.2005.07.007.
[84] P. Mpountoukas, A. Pantazaki, E. Kostareli, P. Christodoulou, D. Kareli, *
Corresponding author.
S. Poliliou, C. Mourelatos, V. Lambropoulou, T. Lialiaris, Cytogenetic evaluation
and DNA interaction studies of the food colorants amaranth, erythrosine and E-mail address: [email protected] (M.S. Islam).

11

View publication stats