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An Integrated Permanganate and Ozone Process For The Treatment of Textile
An Integrated Permanganate and Ozone Process For The Treatment of Textile
An Integrated Permanganate and Ozone Process For The Treatment of Textile
a r t i c l e i n f o a b s t r a c t
Article history: Textile dyeing effluent has been the focus of considerable research because of its adverse effects on
Received 23 May 2018 aquatic biota. Here, we present the first comprehensive study of a combined permanganate and ozone
Received in revised form (KMnO4eO3) technique to treat different kinds of textile dyeing wastewater. We investigated the effects
17 July 2018
of process parameters on TOC and COD removal and the toxicity of the wastewater after KMnO4eO3
Accepted 12 August 2018
Available online 16 August 2018
treatment. The synergistic mechanism involved in the KMnO4eO3 process is also discussed. The results
indicate that KMnO4eO3 treatment is efficient in treating many kinds of textile dyeing wastewater. The
TOC, COD, and toxicity were reduced by approximately 70%, 80%, and 34.4e95.5%, respectively, using a
Keywords:
Textile dyeing wastewater
KMnO4 dosage of 1.5 mM, an O3 dosage of 10 mg/L, a pH value of 7, and a reaction time of 30 min.
Organic pollutants Furthermore, biodegradability was increased to 0.33e0.68. The combined use of KMnO4 and O3 provided
Biotoxicity synergetic and complementary advantages. On the one hand, oxidation of pollutants on suspended solid
Ozone surfaces and in the aqueous phase was enhanced by the stirring action of O3 molecule bubbles. On the
Permanganate other hand, small molecular organic compounds and fine particles were coagulated by KMnO4 and its
Cleaner production intermediate oxidations. X-ray photoelectron spectroscopy results indicate that the valence state of
manganese changed after KMnO4eO3 treatment, and the manganese intermediate catalysing O3 process
contributed to the removal of 20% of COD and 19% of TOC. It was therefore determined that the
KMnO4eO3 treatment is a promising method for use in the treatment of textile dyeing wastewater.
© 2018 Elsevier Ltd. All rights reserved.
https://doi.org/10.1016/j.jclepro.2018.08.112
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
J. Liang et al. / Journal of Cleaner Production 204 (2018) 12e19 13
Table 1
Basic information about the four TDPs and different textile dyeing wastewater treatments used.
PC: primary clarifier; AD: aeration digester; AB: aeration basin; SF: sand-filtration; BSB: biochemical sedimentation basin; ESB: end sedimentation; BAF: biological aerated-
filtration; MF: membrane filtration; SB: sedimentation basin.
treatment (Cheng et al., 2016). The alga Desmodesmus subspicatus was measured via UV detection at 525 nm after filtration using a
(D. subspicatus) and the bacterium Vibrio fischeri (V. fischeri) were 0.45 mm membrane. Atomic absorption spectrometry (AAS, Z-2000,
used to assess the toxicity of wastewater after treatment with Hitachi) was employed to determine the Mn content in sludge; a
KMnO4, O3, and KMnO4eO3. There were minimum changes in the scanning electron microscope (SEM) (S-3400N, Hitachi, Japan) was
pH value during this process, and the reaction temperatures of all used to view sludge surface morphologies; a laser particle size
experiments were controlled to room temperature (Nasuhoglu analyser (Eye Tech, Ankersmid, Netherlands) was used to examine
et al., 2018) (which was approximately 298 ± 2 K) to avoid the the sludge particle sizes; infrared spectra were acquired using a
need for a temperature regulating device. All experiments were Nicolet 6700 FT-IR spectrophotometer (Thermo Fisher, USA); X-ray
conducted in triplicate. photoelectron spectroscopy (XPS) (ESCALAB250, Thermo Fisher
Inc.) was used to determine the valence states of Mn; and the
binding energy was calibrated using the C1s peak at 284.8 eV.
2.3. Analytical method
A digital pH meter (pHS-3C, Leici, China) was used to measure 2.4. Toxicity tests
pH; the potassium dichromate method was used to measure COD
concentrations; mixed liquor volatile suspended solid (MLVSS) and Two different organisms, the alga D. subspicatus and the bacte-
mixed liquor suspended solids (MLSS) measurements were con- rium V. fischeri, were used to assess the toxicity of textile dyeing
ducted using standard methods (APHA, 1998); TOC in the sample wastewater after different treatments. As the samples used for
filtrate was determined using a TOC-VCPH analyser (Shimadzu, toxicity analysis had been quenched with hydroxylamine, there
Japan); the concentration of BOD5 was determined by the five-day was no notable toxicity caused by oxidants. Toxicity for V. fischeri
cultivation method (293 ± 1 K); colour was determined using the was determined according to GB/T15441-1995 using a Microtox
dilution method; and the KMnO4 concentration in the wastewater Model DXY-2 Toxicity Analyser (Nanjing, China), and the ability of
J. Liang et al. / Journal of Cleaner Production 204 (2018) 12e19 15
wastewater to inhibit the bioluminescence of V. fischeri within of TOC and COD by KMnO4 treatment.
15 min of exposure was evaluated. A further toxicity test was Fig. 2c and d presents the impacts of KMnO4 dosage on the
conducted using D. subspicatus, following the GB/T 21805-2008 removal of TOC and COD at pH 3 for 30 min. When the KMnO4
guidance. Samples and blank solutions were tested after 72 h of dosage increased from 0.13 to 2 mM, the concentrations of TOC and
exposure, and toxicity was spectrophotometrically expressed via COD decreased to 16, 75, 41, and 28 mg/L and 61, 230, 128, and
UV detection at 680 nm. Toxicity experiments were conducted in 126 mg/L, in TDP1-4, respectively. At high KMnO4 dosages, more
triplicate. EC50 (the concentration of wastewater that inhibits organic pollutants were oxidised and suspended matter was floc-
bioluminescence of V. fischeri within 15 min, or D. subspicatus culated, which reduced the TOC and COD concentrations. However,
growth by 50% after 72 h) was analysed using the linear interpo- TOC and COD's values at a KMnO4 dosage of 2 mM were only
lation method. EC50 was calculated as a dilution factor (x% of marginally lower than those at a dosage of 1.5 mM. This can be
effluent), and the toxicity of each sample was further expressed in attributed to the fact that Mn(III) or Mn(IV) intermediates were
toxic units, TU (unitless), according to Eq. (1) (Raptis et al., 2014): produced when the KMnO4 dosage was excessive, hindering the
reaction (Jiang et al., 2010). On average, 59% of TOC and 57% of COD
TU ¼ 100=EC50 : (1) were removed when the pH value was 3.0 and the KMnO4 dosage
was 1.5 mM. The removal of COD was higher than for pulp and
paper wastewater treatment (which saw COD removal rates of only
43.8%) under the same conditions (Jaafarzadeh et al., 2017). How-
3. Results and discussion
ever, the acidic conditions during the KMnO4 treatment were
inappropriate to treat textile dyeing wastewater.
3.1. Performance of KMnO4 treatment
As KMnO4 exhibits a very high oxidation potential under acidic 3.2. Performance of O3 treatment
conditions, the effect of pH, within a range of 2e7, on the removal of
TOC and COD by KMnO4 was investigated (results are presented in Different influential factors were investigated during O3 treat-
Fig. 2a and b). As the pH increased, there was a significant decrease ment. Concentrations of TOC and COD decreased as the pH
in the removal of TOC and COD; in contrast, the lowest TOC and increased from 3 to 9, but increased slightly as the pH increased
COD concentrations were obtained at pH 2 for TDPs 1e4 (16, 78, 42, from 9 to 11 (Fig. S2a-b). The lowest TOC and COD concentrations
and 28 mg/L, and 60, 230, 130, and 126 mg/L, respectively). It was were obtained at pH 9 for TDPs 1e4 (23, 96, 95, and 46 mg/L, and
also determined that the concentrations at pH 3 were very close to 132, 232, 232, and 184 mg/L, respectively). The O3 decomposition
those at pH 2. Electron exchange was determined using the rate increased as the concentration of hydroxide ions increased
aqueous pH of the reaction system. Under neutral and alkaline because these ions react with O3 molecules and produce OH
conditions, the oxidation potential of KMnO4 was lower (Aleboyeh (Ershov and Morozov, 2009).$OH has a stronger oxidation potential
et al., 2009), and therefore, acidic conditions promoted the removal (2.86 V) than O3 (2.07 V), which elevates pH levels and reduces the
(a) (b)
350
100 TDP 1 TDP 2 TDP 1 TDP 2
TDP 3 TDP 4 TDP 3 TDP 4
300
80
250
TOC (mg/L)
COD (mg/L)
60 200
40 150
100
20
50
2 3 4 5 6 7 2 3 4 5 6 7
pH pH
(c) (d)
TDP 1 TDP 2
100 350 TDP 1 TDP 2
TDP 3 TDP 4
TDP 3 TDP 4
300
80
TOC (mg/L)
250
COD (mg/L)
60
200
40 150
100
20
50
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
KMnO4 dosage (mM) KMnO4 dosage (mM)
Fig. 2. Effects of pH and KMnO4 dosage on TOC and COD removal by KMnO4 for 30 min, with a KMnO4 dosage of 1.5 mM at pH 3.
16 J. Liang et al. / Journal of Cleaner Production 204 (2018) 12e19
O3 concentration, but produces more radical species (Asghar et al., 3.3. Performance of KMnO4eO3 treatment
2015). Although this is advantageous for TOC and COD removal, an
excessive amount of OH can cause chain reactions between OH KMnO4eO3 treatment was assessed in terms of TOC and COD
and$OH or HO2 e, which reduces organic pollutant removal. removal (results are illustrated in Fig. 3a and b) and was found to be
TOC and COD concentrations also decreased as the reaction time effective in treating different kinds of textile dyeing wastewater.
(Fig. S2ced) and O3 dosage (Fig. S2eef) increased. However, there Under neutral conditions, O3 treatment was more effective than
were almost no noticeable differences between the TOC and COD KMnO4 at removing TOC, whereas KMnO4 was more effective at
concentrations at O3 dosages of 10 and 20 mg/L. On average, 35% of removing COD. The concentrations of TOC and COD were lowered
TOC and 39% of COD were removed at a pH of 9.0 and an O3 dosage to 11, 62, 30, and 20 mg/L, and 24, 86, 90, and 76 mg/L, in TDP 1e4,
of 10 mg/L. Less TOC and COD were removed by O3 under alkaline respectively, after KMnO4eO3 treatment for 30 min. The removal
conditions than by KMnO4 under acidic conditions; this is consid- efficiencies for TOC and COD (70% and 80%, on average) were better
ered to be related to the intense oxidative ability of KMnO4 and the than for KMnO4 alone (21% and 27%, on average) or O3 alone (30%
high adsorption potential of MnO2 for several organic pollutants and 23%, on average). In addition, the KMnO4eO3 treatment under
(Liu et al., 2010). Owing to the extreme conditions required for O3 neutral conditions was even more effective than KMnO4 treatment
(pH 9) and KMnO4 (pH 3) treatment and the low removal effi- under strongly acidic conditions or O3 under strongly alkaline
ciencies for TOC and COD, development of a more appropriate conditions. Therefore, KMnO4eO3 treatment provided the com-
method is required. Combined O3 and KMnO4 treatment is thought bined advantages of both KMnO4 and O3 treatments. We consider
to be a suitable method. that these results relate to the strong oxidative ability of KMnO4
and O3, and the insoluble reduction product (MnO2) produced from
(a) (b)
200
Raw wastewater Raw wastewater
180 O3 490 O3
160 KMnO4 KMnO4
KMnO4-O3
420
140 KMnO4-O3
TOC (mg/L)
350
COD (mg/L)
120
100 280
80 210
60
140
40
20 70
0 0
TDP 1 TDP 2 TDP 3 TDP 4 TDP 1 TDP 2 TDP 3 TDP 4
(c) (d)
BOD/COD
60 0.4
0.3
40
0.2
20
0.1
0 0.0
TDP 1 TDP 2 TDP 3 TDP 4 TDP 1 TDP 2 TDP 3 TDP 4
(e) (f)
1000 8
Raw wastewater Raw wastewater
O3 7 O3
800
TU for D.subspicatus
KMnO4 KMnO4
6
TU for V.fischeri
KMnO4-O3 KMnO4-O3
600 5
4
400 3
2
200
1
0 0
TDP 1 TDP 2 TDP 3 TDP 4 TDP 1 TDP 2 TDP 3 TDP 4
Fig. 3. Effects of different treatments at a KMnO4 dosage of 1.5 mM and an O3 dosage of 10 mg/L at pH 7 for 30 min.
J. Liang et al. / Journal of Cleaner Production 204 (2018) 12e19 17
Table 2
XPS results for Mn 2p3/2 in sludge samples.
(a)
COD
Total removal TOC
80 Quenching- OH
.
- - 7.5
Quenching-O2. /HO2.
60 17.1
TOC
COD
40
Fig. 5. Mn 2p regions of XPS spectra for the sludge after (a) KMnO4 treatment and (b)
KMnO4eO3 treatment. Reaction conditions: [KMnO4] ¼ 1.5 mM, [O3] ¼ 10 mg/L, pH ¼ 7, 2.1 1.2
and reaction time ¼ 30 min.
2.3 1.5
20
indicates that these organic pollutants were removed successfully
by the KMnO4eO3 treatment. A peak was also observed at
O3 KMnO4-O3
1644 cm1, corresponding to CeO stretching vibrations (amide I)
(Chon et al., 2012), indicating that compounds containing an amide
functional group can be coagulated by KMnO4eO3 treatment. A (b)
CeH band at 2923 cm1 was also determined, corresponding to the
alkanes group (Ngamlerdpokin et al., 2011). The eOH group and H- 100
Before KMnO4-O3 treatment
bonded group found between 3200 and 3400 relate to metal hy- After KMnO4-O3 treatment
droxides, amines, and carboxylic acid (Pavia et al., 2008). The
complexity of the textile dyeing sludge was therefore confirmed by 90
the various functional groups present in the FTIR spectra.
Transmittance (%)
biodegradability was considerably increased (to 0.33e0.68) after heterogeneous catalytic system and membrane fouling control. J. Hazard Mater.
344, 1198e1208.
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