Chemical Engineering Journal 348 (2018) 67–73

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Chemical Engineering Journal

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

Advanced oxidation processes based on zero-valent aluminium for treating T

textile wastewater
⁎
Jayraj Khatria,b, P.V. Nidheesha, , T.S. Anantha Singhb, M. Suresh Kumara
a
CSIR-National Environmental Engineering Research Institute, Nagpur, Maharashtra, India
b
Department of Civil Engineering, School of Technology, Pandit Deendayal Petroleum University, Gandhinagar, Gujarat, India

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Textile wastewater treatment by ZVAl

based AOPs.
• Enhancement in process efficiency of
3+
ZVAl/O process with Fe , H O and
2 2 2
persulfate addition.
• 97.9% colour, 94.4% COD and 58.3%
ammoniacal nitrogen removal.

A R T I C LE I N FO A B S T R A C T

Keywords: Treatment of textile wastewater by advanced oxidation processes (AOPs) based on zero-valent aluminium (ZVAl)
Advanced oxidation processes were carried out in the present study. COD removal efficiencies of ZVAl/O2, ZVAl/Fe3+/O2, ZVAl/Fe3+/O2/
Zero-valent aluminium H2O2 and ZVAl/Fe3+/O2/persulfate processes were monitored and optimized. Colour and ammoniacal nitrogen
Textile wastewater removal efficiencies of each process at the optimal operating conditions were compared. Pollutant removal
Hydroxyl radical
efficiencies of AOPs were followed the order as: ZVAl/Fe3+/O2/H2O2 > ZVAl/Fe3+/O2/persulfate > ZVAl/
Sulfate radical
Fe3+/O2 > ZVAl/O2. Maximum COD, colour and ammoniacal nitrogen removal efficiencies of ZVAl-based
AOPs were found as 97.9%, 94.4% and 58.3%, respectively at 1 g/L ZVAl, 0.5 g/L Fe3+, 6.7 g/L H2O2 and after
3 h of contact time. External addition of tert-butyl alcohol to the processes revealed that in-situ hydroxyl and
sulfate radicals are the main oxidants responsible for the oxidation of pollutants. Overall, ZVAl-based AOPs are
efficient for treating effluents generating from textile industry.

1. Introduction is dangerous to aquatic life and human beings. Textile industries are
one of the major sources of water pollution. The textile dye industry
Environmental pollution increases day by day due to industrial ac- effluents contains organic and inorganic salts, dyes, and heavy metals
tivities which is a worldwide problem. Industries are polluting the en- [2,3]. Moreover, 10–15% of the dyes used in textile industry enter into
vironment directly or indirectly [1]. Air, water, land, living organisms, the environment as wastes [4,5]. As textile wastewater is toxic, muta-
plants, animals etc. get affected due to pollution generated through genic and carcinogenic due to presence of dyes [6,7], it is undesirable
industries. When industrial wastewater is discharged in water stream, it for any use. The physicochemical methods like adsorption [8–10],

⁎
Corresponding author.
E-mail address: [email protected] (P.V. Nidheesh).

https://doi.org/10.1016/j.cej.2018.04.074
Received 5 February 2018; Received in revised form 7 April 2018; Accepted 12 April 2018
Available online 27 April 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
J. Khatri et al. Chemical Engineering Journal 348 (2018) 67–73

coagulation [11] and membrane processes [12], electrochemical se- concentrations were changed from 0.5 g/L to 2 g/L. ZVAl/Fe3+/O2/
paration methods [13–15] and biological treatment methods [16,17] H2O2 and ZVAl/Fe3+/O2/persulfate processes were carried out by
are found effective for the removal of dyes from water medium, while changing the concentrations of hydrogen peroxide (1.3 g/L, 4 g/L,
these methods are in-effective for the mineralization of dyes and other 5.3 g/L and 6.7 g/L) and persulfate (0.18 g/L, 0.36 g/L, 0.75 g/L and
recalcitrant compounds present in textile wastewater [18]. 1 g/L), respectively for the optimal operating condition of ZVAl/Fe3+/
Advanced oxidation processes (AOPs) are the effective and efficient O2 process. Aeration was continued till the end of the experiments.
method of treating water and wastewater. AOP is used for removing Samples were collected at regular interval and the removal efficiency of
toxic and non-biodegradable matters present in wastewater [19]. As process was monitored by checking residual COD of treated waste-
compared to conventional treatment techniques AOPs are more effi- water. All the experiments were conducted at room temperature. COD
cient and capable of degrading recalcitrant organic pollutants. In AOPs removal efficiency, colour reduction and ammoniacal nitrogen removal
organic matters are removed by oxidation through generated hydroxyl efficiency were determined using following formula:
or sulfate radicals [20,21]. AOPs such as ozonation [22,23], photo- Initial COD−COD at time t
catalysis [24–26], Fenton [27,28], electro-Fenton [29–31], anodic COD removal efficiency(%) = × 100
Initial COD (1)
oxidation [32,33], photo-Fenton [34,35], peroxicoagulation [36,37],
persulfate oxidation [28,38], sonochemical methods [39,40], hydro- Absorbance of sample at time t
Colour reduction =
dynamic cavitation [41–43] etc. were found very effective for the Absorbance ofwastewater (2)
complete mineralization of dyes from water medium and treatment of
real textile wastewater. Performances of these AOPs for dye removal Ammonical nitrogen removal efficiency(%)
from aqueous medium are well reviewed and documented [15,44–49]. Initial concentration−Final concentration
= × 100
Zero-valent metal based AOPs are emerging field in water and Initial concentration (3)
wastewater treatment. Different kind of zero-valent metals like iron,
nickel, copper, aluminium, magnesium, etc. are available for the 3. Result and discussions
treatment of water and wastewater [50]. Similar to other hetero-
geneous AOPs, zero-valent metal based AOPs have several advantages 3.1. Characteristics of textile wastewater
over homogeneous AOPs such as reusability and effective operation in
wide pH conditions [45]. From last decade, zero-valent aluminium The characteristics of textile wastewater are: pH 7.10–7.80, COD
(ZVAl) got attention for treating contaminated water [51]. Bokare and 2155 mg/L, BOD 500 mg/L, ammoniacal nitrogen 699 mg/L, chloride
Choi [52] reported in first time the ZVAl-based AOP for water and 1463 mg/L, total dissolved solids 5190 mg/L and total suspended solids
wastewater treatment. It has been reported the ZVAl-based AOPs are 513 mg/L. BOD/COD ratio of raw wastewater was found as 0.23. Thus,
effective for the removal of various water and wastewater pollutants biological wastewater treatment methods are not a feasible solution.
like 4-chlorophenol [52], triton X-45 [53], phenol [52], iopamidol AOPs are the best option to treat such types of wastewater as mentioned
[54], dichloroacetate [52], nitrobenzene [52], etc. earlier.
Textile wastewater treatment capacity of various ZVAl-based AOPs
was checked in the present study. ZVAl/O2, ZVAl/Fe3+/O2, ZVAl/ 3.2. ZVAl/O2 process
Fe3+/O2/H2O2 and ZVAl/Fe3+/O2/persulfate processes were con-
sidered. The performance of ZVAl was checked on the basis of COD, ZVAl can generate hydroxyl radicals as in the Eqs. (4) and (5). In
colour and ammoniacal nitrogen removal. acidic medium and in the presence of dissolved oxygen, ZVAl generates
hydrogen peroxide in the water medium and further ZVAl reacts with
2. Materials and methods in-situ generated hydrogen peroxide to produce hydroxyl radicals.
These reactions are reported in first time by Bokare and Choi [52]. Lin
2.1. Materials et al. [56] reported that pH 2 is the ideal conditions for generating
hydrogen peroxide by aerating ZVAl and subsequent production of
Aluminium fine powder (98% extra pure) from LobaChemie, ferric hydroxyl radicals. Similarly, Zhang et al. [57], Liu et al. [58] and Fan
chloride, potassium persulfate, sulfuric acid and hydrogen peroxide et al. [59] observed higher pollutant removal efficiency for ZVAl/O2
from Merck were used for the experiments. All the chemicals were used process at pH near to 2. Similar to the previously published articles,
without further purification. Deionized water was used for preparing COD removal from textile wastewater by ZVAl/O2 process was ex-
reagents. amined at pH 2 and the observed results are shown in Fig. 1. Initially
the experiments were carried out at ZVAl dosage of 1 g/L and 33.9% of
2.2. Textile wastewater COD removal was observed at the end of 3 h reaction time. Experiments
were also carried out to test the COD removal by aeration and ZVAl
Raw textile wastewater was collected in a 20 L capacity plastic without aeration. Aeration is efficient to remove 25% of COD from
container from a textile industry situated in Ahmadabad, Gujarat, India. textile wastewater. COD removal efficiency of ZVAl (in the absence of
The textile wastewater was characterised as per standard methods [55]. air) was observed as 21.3%, which is significantly lesser than aerated
Colour of wastewater was monitored at 500 nm using Microprocessor process. The reason behind lower efficiency of ZVAl without aeration is
UV–visible spectrophotometer (LT – 290, Labstronics, India). mainly attributed to lesser amount of dissolve oxygen in the water
medium and which leads to the lower hydrogen peroxide and hydroxyl
2.3. Experimental procedure radical productions. These results indicate the importance of oxygen for
the generation of hydroxyl radicals, as explained by Bokare and Choi
Initially, pH of textile wastewater was maintained to the required [52]. The authors observed insignificant removal of 4-chlorophenol in
level using 1 N sulfuric acid. 500 mL of the solution was taken in a the absence of oxygen and the removal was enhanced significantly with
1000 mL glass beaker. Required amount of ZVAl was added and aera- the aeration.
tion provided using an aquarium pump. ZVAl/O2 process experiments
were carried out by varying ZVAl dosages as 1 g/L, 4 g/L and 6 g/L. In 2Al 0 + 3O2 + 6H+ → 2Al3 + + 3H2 O2 (4)
order to find the best combination and efficiency, both ZVAl dosage and
ferric ion concentration were varied for ZVAl/Fe3+/O2 process. ZVAl
Al0 + 3H2O2 →Al3+ + 3OH− + 3HO% (5)
dosages of 1 g/L and 2 g/L were considered, while ferric ion

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J. Khatri et al. Chemical Engineering Journal 348 (2018) 67–73

of hydroxyl radicals is responsible for the increased COD removal of

textile wastewater. Ferric ions undergo Fenton reactions as given in the
Eqs. (6) and (7). Externally added ferric ions react with in-situ gener-
ated hydrogen peroxide and generate ferrous ions and hydroperoxyl
radicals in water medium. Ferrous ions generated from this reaction
further react with in-situ- generated hydrogen peroxide and produce
hydroxyl radicals. Thus, the pollutants were removed by the attack of
hydroxyl radicals generated via Fenton reactions and by ZVAl/O2
process. Similar results were observed by Zhang et al. [57] for the re-
moval of acetaminophen from water medium. The authors [57] re-
ported that time required for complete acetaminophen removal was
reduced from 16 h to 3 h with the addition of 100 µM ferric ions. These
results indicate that rate of hydroxyl radical generation via Fenton re-
action is quite higher than that of in-situ hydroxyl radical generation
via in ZVAl/O2 process.

Fe3+ + H2 O2 →Fe2+ + OOH% + H+ (6)

%
Fe 2+
+ H2 O2 →Fe 3+
+ OH + H +
(7)

Fig. 1. COD removal from textile wastewater by ZVAl/O2 process and effect of Further increase in ferric ion dosage from 0.5 g/L to 1.0 g/L de-
ZVAl dosage on its performance. creased the COD removal efficiency of ZVAl/O2 process. COD removal
after 1 h of reaction time was observed as 33.9%. This reduction with
increase in ferric ion dosage is mainly due to the hydroxyl radicals
Further increase in ZVAl dosage increased the COD removal effi-
scavenging reactions occurred in the system. The hydrogen peroxide
ciency of ZVAl/O2 process, as shown in Fig. 1. COD removal efficiency
generation is constant as ZVAl dosage (1.0 g/L) is constant for both the
of the process was increased to 40.6% and 46.5% for an initial ZVAl
experiments. Hydroxyl radical generation via Fenton reaction is rapid
concentration of 4.0 g/L and 6.0 g/L, respectively. This indicates the
than in-situ generation via aeration of ZVAl as observed from the above
increase in hydroxyl radical production with increase in ZVAl con-
result. Thus, the excess ferrous ions (with the addition of 1.0 g/L ferric
centration.
ions) react with in-situ generated hydroxyl radicals as in the Eq. (8).
Since, oxygen is important for generation of radicals in water
Experiments were further conducted at elevated ZVAl concentration
medium, further experiments are carried out by supplying air.
(2.0 g/L) and observed similar results as in the case of 1.0 g/L ZVAl.
Maximum COD removal efficiency was observed for 2.0 g/L ZVAl and
1.0 g/L ferric ions. After 3 h of experiments COD removal efficiency was
3.3. ZVAl/Fe3+/O2 process
observed as 54.9%. But, the increase in removal efficiency for 2.0 g/L
ZVAl and 1.0 g/L ferric ions is very less compared to that of 1.0 g/L
In zero-valent metal based advanced oxidation processes, the ad-
ZVAl and 0.5 g/L ferric ions. Therefore, 1.0 g/L ZVAl and 0.5 g/L ferric
dition of external catalyst plays an important role in treatment. In the
ions were considered for further experiments.
present study, ferric ions were used as a catalyst with ZVAl to treat
textile wastewater. Hsu et al. [60] observed significant improvement in Fe2+ + OH% →Fe3+ + OH− (8)
arsenite oxidation with ferric ion addition to ZVAl/O2 process. Fig. 2
shows the efficiencies of ZVAl/Fe3+/O2 process at various concentra-
tion of ferric ions. COD removal efficiency in ZVAl/O2 process with the 3.4. ZVAl/Fe3+/O2/H2O2 process
addition of 0.5 g/L ferric ions was increased from 30.2% to 44.8%
within 1 h. The contribution of ferric ions with ZVAl in the generation Textile wastewater treatment efficiency of ZVAl/O2 and ZVAl/
Fe3+/O2 processes were found as very less as expected. External ad-
dition of oxidant and subsequent generation of radicals is the best
method to improve the performance of ZVAl-based AOPs. Hydrogen
peroxide is one of the efficient oxidants which can generate hydroxyl
radicals in the water medium. Dogan et al. [61] observed a significant
increase in Bisphenol A removal efficiency of ZVAl/O2 process with the
external addition of hydrogen peroxide. The enhancement in the per-
formance of ZVAl/Fe3+/O2 process with the addition of hydrogen
peroxide is depicted in Fig. 3. From the figure, it can be seen that hy-
drogen peroxide addition has a significant role in the enhancement of
textile wastewater treatment. With the external addition of 1.3 g/L
hydrogen peroxide (1:0.5:1.3 in Fig. 3) the COD removal efficiency of
ZVAl/Fe3+/O2 process has improved from 49.5% to 89.1% after 3 h of
reaction time. This improved efficiency of ZVAl-based AOPs with ex-
ternal hydrogen peroxide addition is mainly attributed by the enhanced
production of hydroxyl radicals as in the Eq. (5). It can also be con-
cluded that hydrogen peroxide production in ZVAl/O2 process is very
less in textile wastewater. This is very clear from the COD removal
efficiency of ZVAl-based AOPs with and without external hydrogen
peroxide addition. External hydrogen peroxide addition improved the
treatment efficiency of ZVAl/Fe3+/O2 approximately two times with
Fig. 2. Textile wastewater treatment efficiency of ZVAl/Fe3+/O2 process. Ratio the addition of 1.3 g/L of hydrogen peroxide.
given in figure: ZVAl dosage (g/L): Fe3+ concentration (g/L). Further increase in hydrogen peroxide concentration did not

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J. Khatri et al. Chemical Engineering Journal 348 (2018) 67–73

Fig. 3. COD removal efficiency of ZVAl/Fe3+/O2/H2O2 process. Ratio given in Fig. 4. COD removal efficiency of ZVAl/Fe3+/O2/persulfate process. Ratio
figure: ZVAl dosage (g/L): Fe3+ concentration (g/L): H2O2 concentration (g/L). given in figure: ZVAl dosage (g/L): Fe3+ concentration (g/L): persulfate con-
centration (g/L).

improve much the treatment efficiency of ZVAl/Fe3+/O2/H2O2 pro-

cess. The COD removal efficiency of the process was reached to 97.9% 3.5. ZVAl/Fe3+/O2/persulfate process
with 6.7 g/L external hydrogen peroxide (1:0.5:6.7 in Fig. 3) addition.
This insignificant improvement at higher hydrogen peroxide con- Persulfate is another oxidant which undergoes decomposition in the
centration is mainly due to the reaction between externally added hy- presence of heavy metals, heat, ultrasound etc. It has been reported that
drogen peroxide and in-situ generated hydroxyl radicals as in the Eq. ZVAl is efficient to decompose persulfate and to generate sulfate radi-
(9). Similar to this reaction, other scavenging reaction like re- cals in water medium as in Eq. (11) [53]. Thus in a ZVAl/O2/persulfate
combination of hydroxyl radicals also occurs at higher hydrogen per- process, organic pollutants are degraded by the attack of hydrogen
oxide concentration (Eq. (10)) [62]. Similar result was observed by peroxide, hydroxyl radical and sulfate radical. In the present study,
Laiju et al. [63] for the treatment of landfill leachate by heterogeneous experiments were carried out by adding persulfate in ZVAl/O2/Fe3+
Fenton process. Even though almost complete COD removal (97.9% at process and effect of persulfate concentration on COD removal effi-
1:0.5:6.7) was achieved at the higher amount of hydrogen peroxide, but ciency was evaluated by varying persulfate concentration. The obtained
as hydrogen peroxide is costly, it is not feasible to use higher amount of results are depicted in Fig. 4. COD removal efficiency of the process was
hydrogen peroxide. It can be possible to use hydrogen peroxide in an increased with increase in persulfate dosage, but the COD removal ef-
optimum quantity which lowers down the value of COD to the effluent ficiency was observed as almost constant at higher persulfate dosages.
discharge limit.
2Al0 + S2O82− + 6H+ + 1.5O2→2Al 3+
+ 2SO4%− + 3H2O (11)
% %
H2O2 + OH →H2O + HO2 (9)
Externally added 0.18 g/L persulfate dosage (1:0.5:0.18 in Fig. 4)
OH% + OH% →H2O2 (10) increased COD removal efficiency of ZVAl/Fe3+/O2 process from
49.5% to 71.1% at the end of 3 h reaction time. This increased effi-
Experiments were also carried out to check the contribution of ZVAl ciency of ZVAl-based AOPs is mainly attributed to the additional sulfate
and ferric ions for this treatment enhancement. COD removal effi- radicals generated in the water medium. It has been reported that
ciencies of ZVAl/O2/H2O2 (1:0:1.3 in Fig. 3) and Fe3+/O2/H2O2 sulfate radicals are more efficient that hydroxyl radicals for the mi-
(0:0.5:1.3 in Fig. 3) processes are also shown in Fig. 3. After 1 h, the neralization of dyes from aqueous medium [28]. This is mainly due to
COD removal efficiency of ZVAl/Fe3+/O2/H2O2 (1:0.5:1.3 in Fig. 3) longer life span of sulfate radicals than that of hydroxyl radicals [20].
process was observed as 84.5% while that of ZVAl/O2/H2O2 (1:0:1.3 in Thus, sulfate radicals play a major role for the degradation of con-
Fig. 3) and Fe3+/O2/H2O2 (0:0.5:1.3 in Fig. 3) were observed as 60.2% taminants in ZVAl/Fe3+/O2/persulfate process. Further increase in the
and 75.3%, respectively. In ZVAl/Fe3+/O2/H2O2 process ZVAl and dosage of persulfate to 0.36 g/L, 0.75 g/L and 1.0 g/L increased COD
Fe3+ ions generate more hydroxyl radicals as compared to ZVAl/O2/ removal efficiency of the process to 73.1%, 74.9% and 78%, respec-
H2O2 and Fe3+/O2/H2O2 processes. The COD removal efficiency of tively. Increase in COD removal efficiency of the process at 1.0 g/L
ZVAl/O2 process increased with the external addition of 1.3 g/L H2O2 persulfate is very less compared to 0.18 g/L persulfate. This is mainly
(1:0:1.3 in Fig. 3) from 30.2 to 60.2% after 1 h. Similar results were due to the scavenging reactions occurring in the system at elevated
observed by Arslan-Alaton et al. [53] that external addition of H2O2 persulfate concentration as in the Eqs. (12) and (13) [65]. Arslan-
enhances the removal efficiency of Triton X-45 in the water medium Alaton et al. [53] also observed similar results for the degradation of
from 38% to 76%. Triton X-45 from the water medium.
COD removal efficiency only with 1.3 g/L H2O2 (0:0:1.3 in Fig. 3)
addition was observed as 58.6% after 1 h and it remained constant at SO4−% + SO4−% →2SO42− (12)
the end of 3 h of experiment. The oxidative potential of hydroxyl ra-
SO−% + S2O82− →S2O8− + SO42− (13)
dicals is 2.8 V and H2O2 is 1.76 V [64,46]. Therefore, the in-situ pro-
duced hydroxyl radicals are responsible for the degradation of con- Experiments were also carried out to check the contribution of ZVAl
taminants at the initial stage. The reason behind the constant COD and ferric ions for this treatment enhancement. COD removal effi-
removal efficiency is the unavailability of hydroxyl radicals after 1 h. ciencies of ZVAl/O2/persulfate (1:0:0.18 in Fig. 4) and Fe3+/O2/per-
sulfate (0:0.5:0.18 in Fig. 4) processes are also shown in Fig. 4. After 3 h

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Fig. 6. Ammoniacal nitrogen removal efficiencies of ZVAl/O2 (1.0 g/L ZVAl),

ZVAl/Fe3+/O2 (1.0 g/L ZVAl and 0.5 g/L Fe3+), ZVAl/Fe3+/O2/H2O2 (1.0 g/L
ZVAl, 0.5 g/L Fe3+, and 6.7 g/L H2O2), and ZVAl/Fe3+/O2/persulfate (1.0 g/L
ZVAl, 0.5 g/L Fe3+, and 0.75 g/L persulfate) processes.
Fig. 5. Colour removal efficiencies of ZVAl/O2 (1.0 g/L ZVAl), ZVAl/Fe3+/O2
(1.0 g/L ZVAl and 0.5 g/L Fe3+), ZVAl/Fe3+/O2/H2O2 (1.0 g/L ZVAl, 0.5 g/L
to hydroxyl radicals, sulfate radicals are also effective to remove am-
Fe3+, and 6.7 g/L H2O2), and ZVAl/Fe3+/O2/persulfate (1.0 g/L ZVAl, 0.5 g/L
moniacal nitrogen from water medium. Ammoniacal nitrogen removal
Fe3+, and 0.75 g/L persulfate) processes.
efficiency of ZVAl/Fe3+/O2/persulfate process (56.3%) was also found
near to that of ZVAl/Fe3+/O2/H2O2 process. This higher removal effi-
of reaction, COD removal efficiency for ZVAl/Fe3+/O2/persulfate ciency of ZVAl/Fe3+/O2/persulfate process is mainly due to the pre-
process was observed as 71.1% for persulfate concentration of 0.18 g/L. sence of both sulfate and hydroxyl radicals. Apart from all, oxidation
Similar to this condition, COD removal efficiency of ZVAl/O2/persul- potential of sulfate radicals is very near to that of hydroxyl radicals
fate and Fe3+/O2/persulfate processes were observed as 66.1% and [20]. Heat activated persulfate process can remove ammoniacal ni-
60.4%, respectively. In ZVAl/Fe3+/O2/persulfate process ZVAl and trogen completely from landfill leachate [69]. Yang et al. [70] observed
Fe3+ ions generates more sulfate radicals and hydroxyl radicals as 83% ammoniacal nitrogen removal using zero-valent iron activated
compare to ZVAl/O2/persulfate and Fe3+/O2/persulfate processes. The peroxymonosulfate process.
active participation of sulfate radicals for degradation of contaminants
in ZVAl/O2/persulfate process result in more COD removal than ZVAl/ 3.7. Effect of tert- butyl alcohol addition
O2 and ZVAl/Fe3+/O2processes. COD removal efficiency of Fe3+/O2/
persulfate process is also more than that of ZVAl/O2 and ZVAl/Fe3+/O2 Effect of tert- butyl alcohol addition on the performance of ZVAl/
processes, but the COD removal efficiency remained almost constant. Fe3+/O2/H2O2 and ZVAl/Fe3+/O2/persulfate processes were examined
This is mainly attributed due to the lesser ferric to ferrous ion trans- by adding 0.1 M tert- butyl alcohol to each process. Both ZVAl-based
formation rate, which results in lesser subsequent decomposition of AOPs were operated at optimal conditions and the observed results are
persulfate [66]. shown in Fig. 7. Form the figure, it can be seen that the efficiency of
both AOPs were suppressed by the addition of tert- butyl alcohol. In-
3.6. Colour and ammoniacal nitrogen removal significant COD and colour removals were observed even after 3 h of
reaction time. This indicates the production of hydroxyl and sulfate
The colour removal efficiency of each ZVAl-based AOPs were also radicals in the treatment system. Tert- butyl alcohol acts as a scavenger
monitored at the optimal condition and are shown in Fig. 5. Colour for hydroxyl as well as sulfate radicals. Similar to these results, Chen
removal efficiency of the process were followed the order as ZVAl/ and Carroll [71] observed reduced performance of persulfate oxidation
Fe3+/O2/H2O2 > ZVAl/Fe3+/O2/persulfate > ZVAl/Fe3+/ process with ethanol addition.
O2 > ZVAl/O2, which is same as that of COD removal. The colour
removal in ZVAl/O2 (1.0 g/L ZVAl), ZVAl/Fe3+/O2 (1.0 g/L ZVAl and 4. Conclusions
0.5 g/L Fe3+), ZVAl/Fe3+/O2/H2O2 (1.0 g/L ZVAl, 0.5 g/L Fe3+, and
6.7 g/L H2O2), and ZVAl/Fe3+/O2/persulfate (1.0 g/L ZVAl, 0.5 g/L ZVAl-based AOPs were found effective for COD removal from textile
Fe3+, and 0.75 g/L persulfate) processes were observed as 72.4%, wastewater treatment. COD removal efficiency of the processes were
79.3%, 94.4% and 84.3%, respectively. Colour removal efficiency of the followed the order as ZVAl/Fe3+/O2/H2O2 > ZVAl/Fe3+/O2/
process is mainly by the attack of hydroxyl and sulfate radicals. persulfate > ZVAl/Fe3+/O2 > ZVAl/O2. The colour removal effi-
Ammoniacal nitrogen removal efficiency of each process at optimal ciency of the processes were also followed the order same as COD re-
condition is shown in Fig. 6. Ammoniacal nitrogen removal efficiency moval efficiency. The highest colour removal efficiency of 94.4% was
of ZVAl/O2, ZVAl/Fe3+/O2 and ZVAl/Fe3+/O2/H2O2 processes were achieved for an external addition of 6.7 g/L hydrogen peroxide with
found as 34.3%, 48.8%, and 58.3%, respectively. This enhanced am- 1.0 g/L ZVAl and 0.5 g/L Fe3+. The ammoniacal nitrogen removal ef-
moniacal nitrogen removal efficiency of these processes is mainly due ficiency under optimal condition of ZVAl/Fe3+/O2/H2O2 and ZVAl/
to hydroxyl radicals generated in the system. Several authors reported Fe3+/O2/persulfate processes were observed almost same while ZVAl/
efficient ammoniacal nitrogen removal by hydroxyl radical based ad- Fe3+/O2 and ZVAl/O2 processes had lower removal efficiency.
vanced oxidation processes, even from real wastewater. Hydrodynamic Moreover, the addition of tert-butyl alcohol in wastewater in ZVAl/
cavitation is capable of removing ammoniacal nitrogen up to 85% from Fe3+/O2/H2O2 and ZVAl/Fe3+/O2/persulfate processes revealed the
chemical fertilizer industry wastewater [67]. Wang et al. [68] observed generation of hydroxyl and sulfate radicals in aqueous solution and
94.2% ammoniacal nitrogen removal from biologically treated landfill their importance in the removal of contaminants from the textile was-
leachate nanofiltration concentrate by electro-Fenton oxidation. Similar tewater. From the observed results, it can be concluded that use of

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[8] V.K. Gupta, Suhas, Application of low-cost adsorbents for dye removal – a review, J.
Environ. Manage. 90 (2009) 2313–2342.
[9] V.K. Gupta, R. Kumar, A. Nayak, T.A. Saleh, M.A. Barakat, Adsorptive removal of
dyes from aqueous solution onto carbon nanotubes: a review, Adv. Colloid Interface
Sci. 193–194 (2013) 24–34.
[10] P. Sharma, H. Kaur, M. Sharma, V. Sahore, A review on applicability of naturally
available adsorbents for the removal of hazardous dyes from aqueous waste,
Environ. Monit. Assess. 183 (2011) 151–195.
[11] A.K. Verma, R.R. Dash, P. Bhunia, A review on chemical coagulation/flocculation
technologies for removal of colour from textile wastewaters, J. Environ. Manage. 93
(2012) 154–168.
[12] W.-J. Lau, A.F. Ismail, Polymeric nanofiltration membranes for textile dye waste-
water treatment: preparation, performance evaluation, transport modelling, and
fouling control — a review, Desalination 245 (2009) 321–348.
[13] T.S. Anantha Singh, S.T. Ramesh, New trends in electrocoagulation for the removal
of dyes from wastewater: a review, Environ. Eng. Sci. 30 (2013) 333–349.
[14] V. Khandegar, A.K. Saroha, Electrocoagulation for the treatment of textile industry
effluent – a review, J. Environ. Manage. 128 (2013) 949–963.
[15] C.A. Martínez-Huitle, E. Brillas, Decontamination of wastewaters containing syn-
thetic organic dyes by electrochemical methods: a general review, Appl. Catal. B
Environ. 87 (2009) 105–145.
[16] R.G. Saratale, G.D. Saratale, J.S. Chang, S.P. Govindwar, Bacterial decolorization
and degradation of azo dyes: a review, J. Taiwan Inst. Chem. Eng. 42 (2011)
138–157.
[17] E. Forgacs, T. Cserháti, G. Oros, Removal of synthetic dyes from wastewaters: a
review, Environ. Int. 30 (2004) 953–971.
[18] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Remediation of dyes in textile
effluent: a critical review on current treatment technologies with a proposed al-
ternative, Bioresour. Technol. 77 (2001) 247–255.
[19] P.S. Roshini, R. Gandhimathi, S.T. Ramesh, P.V. Nidheesh, Combined electro-fenton
and biological processes for the treatment of industrial textile effluent: miner-
alization and toxicity analysis, J. Hazard., Toxic, Radioact. Waste 21 (2017)
4017016.
[20] P.V. Nidheesh, Graphene-based materials supported advanced oxidation processes
for water and wastewater treatment: a review, Environ. Sci. Pollut. Res. 24 (2017)
27047–27069.
[21] P.V. Nidheesh, M. Zhou, M.A. Oturan, An overview on the removal of synthetic dyes
from water by electrochemical advanced oxidation processes, Chemosphere 197
(2018) 210–227.
[22] M. Muthukumar, D. Sargunamani, N. Selvakumar, J. Venkata Rao, Optimisation of
ozone treatment for colour and COD removal of acid dye effluent using central
composite design experiment, Dyes Pigm. 63 (2004) 127–134.
[23] S. Venkatesh, K. Venkatesh, A.R. Quaff, Dye decomposition by combined ozonation
and anaerobic treatment: cost effective technology, J. Appl. Res. Technol. 15 (2017)
340–345.
[24] P. Mahata, T. Aarthi, G. Madras, S. Natarajan, Photocatalytic degradation of dyes
and organics with nanosized GdCoO3, J. Phys. Chem. C 111 (2007) 1665–1674.
Fig. 7. Effect of tert-butyl alcohol addition on ZVAl/Fe3+/O2/H2O2 (1.0 g/L [25] S.K. Kansal, N. Kaur, S. Singh, Photocatalytic degradation of two commercial re-
ZVAl, 0.5 g/L Fe3+, and 6.7 g/L H2O2), and ZVAl/Fe3+/O2/persulfate (1.0 g/L active dyes in aqueous phase using nanophotocatalysts, Nanoscale Res. Lett. 4
(2009) 709–716.
ZVAl, 0.5 g/L Fe3+, and 0.75 g/L persulfate) processes.
[26] S. Rani, M. Aggarwal, M. Kumar, S. Sharma, D. Kumar, Removal of methylene blue
and rhodamine B from water by zirconium oxide/graphene, Water Sci. 30 (2016)
51–60.
ZVAl-based AOPs are effective for removing COD, colour and ammo- [27] S. Xavier, R. Gandhimathi, P.V. Nidheesh, S.T. Ramesh, Comparison of homo-
niacal nitrogen from textile wastewater. geneous and heterogeneous Fenton processes for the removal of reactive dye
Magenta MB from aqueous solution, Desalin. Water Treat. 53 (2015) 109–118.
[28] P.V. Nidheesh, R. Rajan, Removal of rhodamine B from a water medium using
Acknowledgments hydroxyl and sulphate radicals generated by iron loaded activated carbon, RSC Adv.
6 (2016) 5330–5340.
Authors are thankful to the Director, CSIR-NEERI, Nagpur, India for [29] P.V. Nidheesh, R. Gandhimathi, N.S. Sanjini, NaHCO3 enhanced Rhodamine B re-
moval from aqueous solution by graphite-graphite electro Fenton system, Sep.
providing encouragement, and kind permission for publishing the ar-
Purif. Technol. 132 (2014) 568–573.
ticle. [30] A. Özcan, M.A. Oturan, N. Oturan, Y. Şahin, Removal of acid orange 7 from water
by electrochemically generated Fenton’s reagent, J. Hazard. Mater. 163 (2009)
References 1213–1220.
[31] P.V. Nidheesh, R. Gandhimathi, S. Velmathi, N.S. Sanjini, Magnetite as a hetero-
geneous electro Fenton catalyst for the removal of Rhodamine B from aqueous
[1] B. Song, G. Zeng, J. Gong, J. Liang, P. Xu, Z. Liu, Y. Zhang, C. Zhang, M. Cheng, solution, RSC Adv. 4 (2014) 5698–5708.
Y. Liu, S. Ye, H. Yi, X. Ren, Evaluation methods for assessing effectiveness of in situ [32] M. Diagne, V.K. Sharma, N. Oturan, M.A. Oturan, Depollution of indigo dye by
remediation of soil and sediment contaminated with organic pollutants and heavy anodic oxidation and electro-Fenton using B-doped diamond anode, Environ. Chem.
metals, Environ. Int. 105 (2017) 43–55. Lett. 12 (2014) 219–224.
[2] A.E. Ghaly, R. Ananthashankar, M. Alhattab, V.V. Ramakrishnan, Production, [33] S. Ammar, M. Asma, N. Oturan, R. Abdelhedi, M.A. Oturan, Electrochemical de-
characterization and treatment of textile effluents: a critical review, J. Chem. Eng. gradation of anthraquinone dye alizarin red: role of the electrode material, Curr.
Process Technol. 5 (2013) 182. Org. Chem. 16 (2012) 1978–1985.
[3] C.D. Raman, S. Kanmani, Textile dye degradation using nano zero valent iron: a [34] S. Xavier, R. Gandhimathi, P.V. Nidheesh, S.T. Ramesh, Comparative removal of
review, J. Environ. Manage. 177 (2016) 341–355. Magenta MB from aqueous solution by homogeneous and heterogeneous photo-
[4] F.I. Hai, K. Yamamoto, K. Fukushi, Hybrid treatment systems for dye wastewater, Fenton processes, Desalin. Water Treat. 57 (2016) 12832–12841.
Crit. Rev. Environ. Sci. Technol. 37 (2007) 315–377. [35] M. Muruganandham, M. Swaminathan, Decolourisation of reactive Orange 4 by
[5] Q. Husain, Potential applications of the oxidoreductive enzymes in the decolor- Fenton and photo-Fenton oxidation technology, Dyes Pigm. 63 (2004) 315–321.
ization and detoxification of textile and other synthetic dyes from polluted water: a [36] P.V. Nidheesh, R. Gandhimathi, Electrolytic removal of Rhodamine B from aqueous
review, Crit. Rev. Biotechnol. 26 (2006) 201–221. solution by peroxicoagulation process, Environ. Sci. Pollut. Res. 21 (2014)
[6] R.O. Cristóvão, A.P.M. Tavares, A.S. Ribeiro, J.M. Loureiro, R.A.R. Boaventura, 8585–8594.
E.A. Macedo, Kinetic modelling and simulation of laccase catalyzed degradation of [37] P.V. Nidheesh, R. Gandhimathi, Effect of solution pH on the performance of three
reactive textile dyes, Bioresour. Technol. 99 (2008) 4768–4774. electrolytic advanced oxidation processes for the treatment of textile wastewater
[7] G. Mishra, M. Tripathy, A critical review of the treatments for decolourization of and sludge characteristics, RSC Adv. 4 (2014) 27946–27954.
textile effluent, Colourage 40 (1993) 35–38. [38] K. Sarath, R. Gandhimathi, S.T. Ramesh, P.V. Nidheesh, Removal of reactive

72
J. Khatri et al. Chemical Engineering Journal 348 (2018) 67–73

magenta-MB from aqueous solution by persulphate-based advanced oxidation Methods 541 (2012).
process, Desalin. Water Treat. 57 (2016) 11872–11878. [56] K. Lin, J. Cai, J. Sun, X. Xue, Removal of 2,4-dichlorophenol by aluminium/O2/acid
[39] P. Gayathri, R. Praveena Juliya Dorathi, K. Palanivelu, Sonochemical degradation system, J. Chem. Technol. Biotechnol. 88 (2013) 2181–2187.
of textile dyes in aqueous solution using sulphate radicals activated by immobilized [57] H. Zhang, B. Cao, W. Liu, K. Lin, J. Feng, Oxidative removal of acetaminophen using
cobalt ions, Ultrason. Sonochem. 17 (2010) 566–571. zero valent aluminum-acid system: efficacy, influencing factors, and reaction me-
[40] K.P. Mishra, P.R. Gogate, Intensification of degradation of aqueous solutions of chanism, J. Environ. Sci. 24 (2012) 314–319.
rhodamine B using sonochemical reactors at operating capacity of 7 L, J. Environ. [58] X. Liu, J.H. Fan, L.M. Ma, Elimination of 4-chlorophenol in aqueous solution by the
Manage. 92 (2011) 1972–1977. bimetallic Al-Fe/O2 at normal temperature and pressure, Chem. Eng. J. 236 (2014)
[41] V.K. Saharan, M.P. Badve, A.B. Pandit, Degradation of reactive red 120 dye using 274–284.
hydrodynamic cavitation, Chem. Eng. J. 178 (2011) 100–107. [59] J.H. Fan, X. Liu, L Ming Ma, EDTA enhanced degradation of 4-bromophenol by Al0-
[42] M.M. Gore, V.K. Saharan, D.V. Pinjari, P.V. Chavan, A.B. Pandit, Degradation of Fe0-O2 system, Chem. Eng. J. 263 (2015) 71–82.
reactive orange 4 dye using hydrodynamic cavitation based hybrid techniques, [60] L.C. Hsu, K.Y. Chen, Y.T. Chan, Y. Deng, C.E. Hwang, Y.T. Liu, S.L. Wang,
Ultrason. Sonochem. 21 (2014) 1075–1082. W.H. Kuan, Y.M. Tzou, MS title: catalytic oxidation and removal of arsenite in the
[43] P.R. Gogate, G.S. Bhosale, Comparison of effectiveness of acoustic and hydro- presence of Fe ions and zero-valent Al metals, J. Hazard. Mater. 317 (2016)
dynamic cavitation in combined treatment schemes for degradation of dye waste- 237–245.
waters, Chem. Eng. Process. Process Intensif. 71 (2013) 59–69. [61] M. Dogan, T. Ozturk, T. Olmez-Hanci, I. Arslan-Alaton, Persulfate and hydrogen
[44] S.P. Ghuge, A.K. Saroha, Catalytic ozonation for the treatment of synthetic and peroxide-activated degradation of bisphenol a with nano-scale zero-valent iron and
industrial effluents – application of mesoporous materials: a review, J. Environ. aluminum, J. Adv. Oxid. Technol. 19 (2016) 266–275.
Manage. 211 (2018) 83–102. [62] C. Walling, Fenton’s reagent revisited, Acc. Chem. Res. 8 (1975) 125–131.
[45] P.V. Nidheesh, Heterogeneous Fenton catalysts for the abatement of organic pol- [63] A.R. Laiju, T. Sivasankar, P.V. Nidheesh, Iron-loaded mangosteen as a hetero-
lutants from aqueous solution: a review, RSC Adv. 5 (2015) 40552–40577. geneous Fenton catalyst for the treatment of landfill leachate, Environ. Sci. Pollut.
[46] P.V. Nidheesh, R. Gandhimathi, S.T. Ramesh, Degradation of dyes from aqueous Res. 21 (2014) 10900–10907.
solution by Fenton processes: a review, Environ. Sci. Pollut. Res. 20 (2013) [64] E. Brillas, I. Sirés, M.A. Oturan, Electro-Fenton process and related electrochem- ical
2099–2132. technologies based on Fenton’s reaction chemistry, Chem. Rev. 109 (2009)
[47] P.V. Nidheesh, R. Gandhimathi, Trends in electro-Fenton process for water and 6570–6631.
wastewater treatment: an overview, Desalination 299 (2012) 1–15. [65] P. Neta, V. Madhavan, H. Zemel, R.W. Fessenden, Rate constants and mechanism of
[48] U.G. Akpan, B.H. Hameed, Parameters affecting the photocatalytic degradation of reaction of sulfate radical anion with aromatic compounds, J. Am. Chem. Soc. 99
dyes using TiO2-based photocatalysts: a review, J. Hazard. Mater. 170 (2009) (1977) 163–164.
520–529. [66] T.T. Asha, R. Gandhimathi, S.T. Ramesh, P.V. Nidheesh, Treatment of stabilized
[49] I.K. Konstantinou, T.A. Albanis, TiO2-assisted photocatalytic degradation of azo leachate by ferrous-Activated persulfate oxidative system, J. Hazard. Toxic,
dyes in aqueous solution: kinetic and mechanistic investigations: a review, Appl. Radioact. Waste 21 (2017) 4016012.
Catal. B Environ. 49 (2004) 1–14. [67] V.M. Bhandari, L.G. Sorokhaibam, V.V. Ranade, Industrial wastewater treatment for
[50] A.D. Bokare, W. Choi, Review of iron-free Fenton-like systems for activating H2O2 fertilizer industry—a case study, Desalin. Water Treat. 57 (2016) 27934–27944.
in advanced oxidation processes, J. Hazard. Mater. 275 (2014) 121–135. [68] Y. Wang, X. Li, L. Zhen, H. Zhang, Y. Zhang, C. Wang, Electro-Fenton treatment of
[51] P.V. Nidheesh, J. Khatri, T.S. Anantha Singh, R. Gandhimathi, S.T. Ramesh, Review concentrates generated in nanofiltration of biologically pretreated landfill leachate,
of zero-valent aluminium based water and wastewater treatment methods, J. Hazard. Mater. 229–230 (2012) 115–121.
Chemosphere 200 (2018) 621–631. [69] Y. Deng, C.M. Ezyske, Sulfate radical-advanced oxidation process (SR-AOP) for si-
[52] A.D. Bokare, W. Choi, Zero-valent aluminum for oxidative degradation of aqueous multaneous removal of refractory organic contaminants and ammonia in landfill
organic pollutants, Environ. Sci. Technol. 43 (2009) 7130–7135. leachate, Water Res. 45 (2011) 6189–6194.
[53] I. Arslan-Alaton, T. Olmez-Hanci, S. Khoei, H. Fakhri, Oxidative degradation of [70] Y. Yang, H. Guo, Y. Zhang, Q. Deng, Analysis on the removal of ammonia nitrogen
Triton X-45 using zero valent aluminum in the presence of hydrogen peroxide, using peroxymonosulfate activated by nanoparticulate zero-valent iron, Chem. Pap.
persulfate and peroxymonosulfate, Catal. Today 280 (2017) 199–207. 71 (2017) 1497–1505.
[54] I. Arslan-Alaton, T. Olmez-Hanci, G. Korkmaz, C. Sahin, Removal of iopamidol, an [71] H. Chen, K.C. Carroll, Metal-free catalysis of persulfate activation and organic-
iodinated X-ray contrast medium, by zero-valent aluminum-activated H2O2 and pollutant degradation by nitrogen-doped graphene and aminated graphene,
S2O82-, Chem. Eng. J. 318 (2017) 64–75. Environ. Pollut. 215 (2016) 96–102.
[55] APHA, Standard methods for the examination of water and wastewater, Stand.

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