Chemical Engineering Journal 218 (2013) 319–326

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Chemical Engineering Journal

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

Pretreatment of dry-spun acrylic fiber manufacturing wastewater by

Fenton process: Optimization, kinetics and mechanisms
Jian Wei a,b, Yonghui Song a,b,⇑, Xiang Tu b, Le Zhao b,c, Erquan Zhi a,b
a
College of Water Science, Beijing Normal University, Xinjiekou Wai Street 19, Beijing 100875, China
b
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Dayangfang 8, Anwai Beiyuan, Beijing 100012, China
c
College of Chemical and Environmental Engineering, China University of Mining and Technology, Xueyuan Rode 11, Beijing 100083, China

h i g h l i g h t s

" Fenton process for the pretreatment of dry-spun acrylic fiber wastewater.
" Process optimization and kinetic study of COD degradation with the Fenton process.
" Fenton process effectively enhanced the biodegradability of DAF wastewater.
" Decomposition of the main pollutants was analyzed by GC–MS, FTIR and EEM.

a r t i c l e i n f o a b s t r a c t

Article history: Fenton process was applied to the pretreatment of wastewater from dry-spun acrylic fiber (DAF) manu-
Received 6 September 2012 facturing. The effects of operating parameters including the Fenton reagent dosage, the initial pH value,
Received in revised form 29 November 2012 and the reaction time on the treatment efficiencies of the Fenton oxidation process were observed. About
Accepted 22 December 2012
47.0% of the chemical oxygen demand (COD) removal efficiency was reached under the optimum condi-
Available online 29 December 2012
tions: hydrogen peroxide of 90.0 mM, ferrous ions of 20.0 mM, pH value of 3.0, and reaction time of
120 min. The COD degradation of the Fenton process followed the pseudo first-order reaction kinetics,
Keywords:
and the apparent activation energy E, was determined to be 41.6 kJ mol1. After the Fenton pretreatment
Acrylic fiber manufacturing wastewater
Fenton
under the optimum reaction conditions, the BOD5/COD ratio of wastewater increased from 0.32 to 0.69,
Kinetic study which was suitable for further biological treatment. The improvement of biodegradability was attributed
GC–MS to the removals of aromatics and some other bio-refractory compounds from the wastewater, as con-
Spectrum analysis firmed by gas chromatography–mass spectrometry (GC–MS), Fourier transform infrared spectroscopy
(FTIR) and fluorescence excitation–emission matrix (EEM) spectroscopy analyses. Fenton process was
proven to be an effective method for the pretreatment of DAF manufacturing wastewater prior to biolog-
ical treatment.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
Over the past decades, the acrylic fiber industry has rapidly pro-
gressed in many developing countries. China acquired the technol-
ogy of dry-spun acrylic fiber (DAF) manufacturing from the
American Dubos in the 1990s. The products of this technology
are welcomed because of their high quality and versatility. How-
ever, the effluents of DAF manufacturing contain amounts of or-
ganic and inorganic contaminants [1]. Some of these pollutants
are toxic and bio-refractory, which may cause serious environmen-
⇑ Corresponding author at: State Key Laboratory of Environmental Criteria and
Risk Assessment, Chinese Research Academy of Environmental Sciences, Dayangf-
ang 8, Anwai Beiyuan, Beijing 100012, China. Tel./fax: +86 10 84928380.
E-mail address: songyh@craes.org.cn (Y. Song).
tal impacts if they are discharged directly into receiving waters
without appropriate treatment.
To improve the biodegradability of DAF manufacturing waste-
water, it is primarily mixed with domestic wastewater generated
from a plant, and then subjected to anaerobic, aerobic, and
activated carbon biological treatments. However, highly toxic com-
pounds are recalcitrant to be biodegraded, and high concentrations
of inorganic salts (e.g., sulfates and sulfites) reduce the efficiency of
anaerobic digestion. High quantities of polymers and colloids in
effluents are also difficult to be biodegraded or precipitated natu-
rally. Effluents of biological treatments still contain high concen-
trations of chemical oxygen demand (COD), ammonia nitrogen,
and toxic compounds. The biochemical process cannot efficiently
remove organic pollutants to meet increasingly strict environmen-
tal standards [1–3]. Thus, an effective step such as pretreatment

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.12.060
320 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326
must be adopted prior to the biological process, to remove refrac-
tory organics and to improve their biodegradability.
Advanced oxidation processes (AOPs) based on the generation
of hydroxyl radicals (OH) are widely used in the treatment or pre-
treatment of bio-refractory industrial wastewater. Among the
AOPs, Fenton process is particularly attractive because of its sim-
plicity and high removal efficiency of recalcitrant pollutants [4,5].
The typical Fenton reagent includes ferrous ions (Fe2+) and hydro-
gen peroxide (H2O2). In acidic conditions, strong oxidative OH is
generated in the catalytic oxidation reaction (1) of H2O2 with
Fe2+. Apart from the main reaction, a series of chain reactions
(2)–(5) involving Fe2+, ferric (Fe3+), H2O2, superoxide, and OH are
also possible. In these reactions, bio-refractory or toxic organic
compounds can be oxidized to biodegradable small molecules or
carbon dioxide and water [6].
Fe2þ þ H2 O2 ! Fe3þ þ OH þ  OH
Fe2þ þ  OH ! Fe3þ þ OH
H2 O2 þ  OH ! HO2 þ H2 O
Fe2þ þ HO2 ! Fe3þ þ HO2
Fe3þ þ HO2 ! Fe2þ þ O2 þ Hþ
According to the existence form of catalyst, the Fenton reaction can
be divided into two types: classical homogeneous Fenton oxidation
and novel heterogeneous Fenton oxidation. Currently, some research-
ers have reported that heterogeneous Fenton oxidation with novel cat-
alyst could offer significant advantages such as high removal efficiency
of organic pollutants, without Fe2+ addition and no iron-containing
sludge generation [7]. However, the activity of catalyst is easily
affected by the influent quality, and the reusability of catalyst is too
poor for long-time operation [8]. Additionally, most heterogeneous
Fenton technologies are still in the stage of laboratory research, which
are difficult to industrial application [9,10]. Compared with heteroge-
neous Fenton oxidation, classical homogeneous Fenton oxidation is
easier for industrial application without special equipment require-
ment. Furthermore, the ferric complex accounting for flocculation
can improve the efficiency of the Fenton process [11]. In recent years,
Fenton oxidation has been extensively studied for the treatment of a
variety of toxic and bio-refractory wastewaters such as chemical man-
ufacturing wastewater [12], pharmaceutical wastewater [13], textile
dying wastewater [14], landfill leachate [15], and so on. Nonetheless,
to the best of our investigation, there is no application of Fenton
process to the pretreatment of DAF manufacturing wastewater.
In this study, the classical homogeneous Fenton process was
used for the pretreatment of DAF manufacturing wastewater gen-
erated from a petrochemical plant in China. The effects of four key
operational parameters, including H2O2 dosage, Fe2+ dosage, pH va-
lue, and reaction time were investigated. Kinetic study using a
modified pseudo first-order model was carried out to determine
the kinetic constants. The biodegradability variation of the waste-
water was evaluated and the main organic pollutants in raw and
treated DAF manufacturing wastewaters were analyzed by gas
chromatography–mass spectrometry (GC–MS). In addition, Fourier
transform infrared spectroscopy (FTIR) and fluorescence excita-
tion–emission matrix (EEM) spectroscopy were used to analyze
main components of wastewater in this study.
2. Materials and methods
2.1. Raw wastewater
The wastewater used in this study was collected from the DAF
manufacturing department of a fiber synthesis plant in Liaoning
Table 1
Characteristics of DAF manufacturing wastewater.
Parameter Unit Value
COD mg O2/L 1091
BOD5 mg O2/L 349
TOC mg/L 410
TN mg/L 160
NH3AN mg/L 21.6
pH – 6.56
Province, northeast China. The samples were stored at 4 °C, trans-
ported to laboratory, and immediately analyzed. The characteris-
tics of the DAF manufacturing wastewater of this study are listed
in Table 1.
ð1Þ
2.2. Experimental process
ð2Þ
Fenton oxidation experiments were conducted in 500 mL batch
ð3Þ reactors at 25 °C with mechanical stirring for continuous mixing of
the reaction system. The pH value was adjusted with 3.0 M H2SO4
solution and 5.0 M NaOH solution. In a typical experiment, a
ð4Þ
weighed amount of FeSO47H2O was dissolved in 300 mL of DAF
manufacturing wastewater under stirring. Fenton oxidation was
ð5Þ
then initiated by the addition of H2O2 solution (30%, w/w). Samples
were withdrawn from the reactor at predetermined intervals, and
the reaction was terminated by adjusting the pH value to 10.0,
which instantaneously consumed the remaining H2O2. Finally, stir-
ring was stopped and the solution was left undisturbed for 30 min
to settle out the flocs. The supernatant was withdrawn and filtered
for analyses.
2.3. Analytical methods
GC–MS was used for organic compound analysis. Prior to GC–
MS measurement, 100 mL of water sample was extracted by HLB
and Envi-18 solid-phase extraction columns. First, the HLB and
Envi-18 columns were sequentially activated with 5 mL of CH2Cl2
(Chromatogram Pure Grade, Merck, USA), CH3OH (Chromatogram
Pure Grade, Merck, USA), and ultrapure water with the flow rate
of 6 mL/min. The HLB column was then eluted with 10 mL mixing
solution of CH2Cl2 and CH3OH (9/1, v/v) for three times, and the
Envi-18 column was eluted with 10 mL mixture solution of hexane
and CH2Cl2 (7/3, v/v) for three times. The eluent was mixed, dehy-
drated with anhydrous sodium sulfate, and concentrated to 0.5 mL
with the aid of nitrogen flow. 1 lL of concentrated liquor was in-
jected to the 7890/5975 GC–MS system (Agilent, USA) equipped
with an HP-5 capillary column with an inner diameter of
0.25 mm and a length of 30.0 m. The GC column was operated in
a temperature programmed mode at 40 °C for 2 min, and then
raised at 5 °C/min to 290 °C (held for 4 min). Analysis was under-
taken with reference to the NIST 05 mass spectral library database.
FTIR was applied to the assessment of the difference of general
functional organic groups in the raw and treated DAF manufactur-
ing wastewater. The FTIR analyses of the samples were conducted
by using a Perkin Elmer 100 FTIR spectrometer with resolution of
4 cm1, in the range of 4000–400 cm1. The samples were first
dried and grinded prior to the FTIR analysis and were prepared
with the discolor technique using a finely ground mixture of
6 mg sample and 300 mg KBr and then pressed into a pellet under
10 tons force for 1 min [16].
EEM spectroscopy was made using a Hitachi F-7000 Fluores-
cence Spectrophotometer equipped with the fluorescence solu-
tions 100,000 for data processing. Excitation and emission slit
widths were set to 5 nm and PMT Voltage to 700 V. The excitation
 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326 321

wavelength was scanned from 200 to 450 nm and the correspond-
ing emission wavelength was recorded from 260 to 500 nm.
Total organic carbon (TOC) was determined by using the Analy-
tik Jena Multi N/C 2100 analyzer. COD, biochemical oxygen de-
mand (BOD5) analysis were conducted according to standard
methods [17] and pH value was measured by the OHAUS Starter
3C pH meter.
3. Results and discussion
3.1. Optimization of process parameters
The pretreatment of DAF manufacturing wastewater was car-
ried out under different operational conditions to optimize the pro-
cess parameters on COD removal efficiency.
redox reaction between high active OH and excess Fe2+ could in-
duce a self-scavenging effect of OH (Eq. (2)), which reduces the
degradation efficiency of pollutants [18].
For industrial application, the cost of reagents is one of the most
important limiting factors. So it is important to reduce the cost of
chemicals and the production of Fe3+ which probably precipitates
as Fe(OH)3. At ferrous ions concentration of 30.0 mM, where
H2O2:Fe2+ was 3:1, the final COD removal efficiency reached the
maximum value, which was only slightly higher than that of fer-
rous ions concentration of 20.0 mM, where H2O2:Fe2+ was 4.5:1.
From the commercial point of view, it is desirable to find a compro-
mised ferrous salt amount with minimized iron sludge production
and improved pollutants removal. So the optimal ferrous dosage
for DAF manufacturing wastewater pretreatment was determined
to be 20.0 mM.

3.1.1. Effect of the Fe2+ dose
To determine the effect of the Fe2+ dose on COD removal effi-
ciency in DAF manufacturing wastewater, Fe2+ concentration was
varied from 5.0 mM to 35.0 mM and the other conditions were
fixed (initial pH value of 3.0, H2O2 concentration of 90.0 mM and
reaction time of 120 min). Fig. 1a shows that the COD removal effi-
ciency significantly increased from 22.5% to 47.3% with the in-
crease of Fe2+ concentration from 5.0 mM to 20.0 mM. However,
further Fe2+ dose increase from 20.0 mM to 30.0 mM did not signif-
icantly improve COD removal. The COD removal efficiency even
slightly dropped when the Fe2+ dose increased to 35.0 mM. These
results indicated that too high Fe2+ concentration did not result
in higher COD removal efficiency. A probable reason was that the
3.1.2. Effect of the H2O2 dose
In the Fenton process, H2O2 is the most important parameter
because it is the source of OH and the main cost for scale-up appli-
cation. The effect of the H2O2 dose (30.0–210.0 mM) on the COD re-
moval efficiency was investigated at an initial pH value of 3.0, Fe2+
dose of 20.0 mM and reaction time of 120 min. Fig. 1b shows the
effect of the H2O2 dose on the COD removal efficiency. The COD re-
moval efficiency increased from 28.5% to 47.3% with the H2O2 dose
increase from 30.0 mM to 90.0 mM. However, the removal effi-
ciency slowly increased from 47.3% to 53.6% in the H2O2 dosage
range of 90.0–210.0 mM.
The occurrence of this phenomenon may be attributed to the
following reasons. Under 90.0 mM H2O2 concentration, the OH

(a) 60 (b) 60

50 50
COD Removal (%)

COD Removal (%)

40 40

30 Initial pH: 3.0 30 Initial pH: 3.0

H2O2: 90.0 mM 2+
Fe : 20.0 mM
Reaction time: 120 min Reaction time: 120 min
20 20

10 10
5 10 15 20 25 30 35 0 30 60 90 120 150 180 210
2+
Fe (mM) H2O2 (mM)

(c)60 (d) 60
50
50
COD Removal (%)

COD Removal (%)

40
40
30
Initial pH: 3.0
30 20 H2O2: 90.0 mM
H2O2 : 90.0 mM;
2+ 2+
Fe : 20.0 mM; Fe : 20.0 mM
20 Reaction time: 120 min 10

0
10
2 3 4 5 6 7 0 20 40 60 80 100 120 140 160 180 200
pH Time (min)

Fig. 1. Effects of different parameters on the COD removal efficiency in Fenton oxidation: (a) Fe2+ dose, (b) H2O2 dose, (c) initial pH, and (d) reaction time.
322 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326

quantity rapidly increased with the increase of H2O2 concentration. 50

Consequently, the oxidation capability of the Fenton system was
enhanced and the COD removal efficiency rapidly increased. How-
40
ever, catalytic Fe2+ was oxidized to Fe3+ by excess H2O2, and the

COD Removal (%)

oxidation capability of the Fenton system decreased. Superfluous
H2O2 acted as a scavenger of the highly potent OH to produce 30
the hydroperoxyl radical ðHO2 Þ, which had a much lower oxidation
ability than OH [19–22]. Thus, the COD removal efficiency did not 20
further increase if the H2O2 addition surpassed the optimum dose
o o
of the reaction system. 10 C 20 C
10 o o
30 C 40 C
3.1.3. Effect of the initial pH value o
50 C
The pH also crucially affects the treatment efficiency of the Fen- 0
ton process. To determine the effect of the initial pH value on the
COD removal efficiency, the initial pH values were varied from 0 20 40 60 80 100 120
2.0 to 7.0 and the other conditions were fixed (H2O2 dose of Time (min)
90.0 mM, Fe2+ dose of 20.0 mM and reaction time of 120 min).
Fig. 2. Effect of COD removal in different temperatures.
The results are shown in Fig. 1c. At pH value of 3.0 the COD re-
moval efficiency reached the highest, and then slightly decreased
with the increase of pH value. COD0
This finding may be due to the significant effect of the pH value ln ¼ kt ð7Þ
COD
on the catalytic activity of Fe2+ in the Fenton reaction system.
When the initial pH was lower than the optimum pH value, Fe2+ where COD0 is the initial COD concentration of the DAF manufactur-
transformed into the complex species [Fe(II)(H2O)6]2+, which re- ing wastewater.
acted more slowly with H2O2 than [Fe(II)(OH)(H2O)5]+, thereby pro- In most Fenton process, the fraction of the initial organic pollu-
ducing fewer OH radicals [23]. At a very low pH value, the reaction tants generated after the chemical oxidation are difficult to be fur-
of Fe2+ with H2O2 was inhibited and OH was scavenged by H+ [24]. ther degraded. These fractions are mainly micromolecule organics
On the other hand, at an initial pH value higher than the optimum which are not oxidizable under the test conditions after an ‘‘infi-
pH, the COD removal efficiency decreased because of the formation nite’’ period (COD1). In this experiment, the Fenton system is al-
of Fe(OH)3, which had a lower catalytic activity for H2O2 decompo- most ineffective for further COD removal after 2.0 h. Therefore,
sition [25–27]. The optimum pH value of the present research was the expression can be modified as:
found to be 3.0, which closely agreed with the values in literature
[28,29]. COD0  COD1
ln ¼ kt ð8Þ
COD  COD1
3.1.4. Effect of the reaction time
The effect of the reaction time on the COD removal efficiency According to Eq. (8), a plot of lnðCOD0  COD1 Þ  lnðCOD 
was investigated under the following conditions: pH value of 3.0, COD1 Þ versus reaction time t will yield a straight line for each
H2O2 dose of 90.0 mM, and Fe2+ dose of 20.0 mM. Fig. 1d shows experiment whose slope is k.
the effect of the reaction time on the COD removal efficiency dur- Fig. 3 shows the pseudo first-order kinetics for the Fenton sys-
ing the Fenton process. The COD removal efficiency rapidly in- tem at different reaction temperature. As can be seen, temperature
creased to 33.7% in the first 30 min, and then slightly increased has a positive impact on COD degradation rate. The k of COD deg-
and reached the maximum of 47.1% at about 120 min. No further radation is significantly affected by reaction temperature, and in-
COD removal increase was observed with further prolonged reac- creases with the increase of temperature from 10 to 50 °C.
tion time. However, the COD removal efficiency was not improved at the
temperature above 30 °C.
3.2. Kinetic study According to the apparent kinetic rate constants at different
temperature, the apparent activation energy E, for the COD
Due to the complexity of the Fenton reaction, it is virtually
impossible to carry out a detailed kinetic study on different indi-
5.0
vidual reactions taking place during the Fenton process. However, o
10 C, k=0.026
o
20 C, k=0.035
ln(COD0-COD ∞)-ln(COD-COD∞)

it is possible to conduct an approximate kinetic study according to o

30 C, k=0.061
o
40 C, k=0.087
some parameters (e.g., COD and TOC) that represents the overall 4.0 o
50 C, k=0.265
organic pollutants [29,30].
Fig. 2 shows the effect of temperature on COD removal effi- 3.0
ciency during Fenton pretreatment of DAF manufacturing waste-
water. This study tried to assess and obtain a set of apparent
2.0
kinetic constants that reflect the COD degradation rate of the Fen-
ton process at different temperature.
In the present study, assuming that COD degradation followed 1.0
pseudo first-order kinetics (Eq. (6)) [30]:
dCOD 0.0
¼ kCOD ð6Þ
dt 0 10 20 30 40 50
Time (min)
where k is the reaction rate coefficient, t is the reaction time and
COD is the COD concentration at the time of t. Eq. (6) can be inte- Fig. 3. Determination of first-order rate constants in the treatment of DAF
grated between t = 0 and t = t, yielding: wastewater by Fenton process at different initial temperature.
 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326 323

degradation by the Fenton process was computed with Arrhenius 1200 0.8
equation. COD

COD, BOD5 (mgO2/L) & TOC (mgC/L)

  BOD5
0.7
E 1000 TOC
k ¼ A0 exp  ð9Þ
RT BOD5/COD
0.6
where A0 is the pre-exponential factor (min1); E is the energy of

BOD5/COD
800
activation (kJ/mol1); R is the ideal gas constant (8.314 J mol1k1);
0.5
T is the absolute reaction temperature (K). The Arrhenius plot of ln k
versus 103/T was shown in Fig. 4. The apparent activation energy 600
(E), obtained from the Arrhenius type plot was found to be 0.4
41.6 kJ mol1, and the pre-exponential factor (A0) value was
4.4  105 min1. Therefore, the Arrhenius form of the COD degrada- 400
0.3
tion can be described as following equation:
!
5 41:6  103 1
200
0 20 40 60 80 100 120
0.2
k ¼ 4:4  10 exp  1
ðmin Þ ð10Þ
8:314  TðK Þ Time (min)

Generally, the reaction activation energy of ordinary thermal Fig. 5. COD, BOD5, TOC and BOD5/COD ratio variation of DAF manufacturing
reactions is in the range of 60 kJ mol1 and 250 kJ mol1 [31,32], wastewater in Fenton’s process (H2O2 = 90.0 mM; Fe2+ = 20.0 mM; pH = 3.0 and
and the result implies that the COD degradation of DAF manufac- reaction time = 120 min).

turing wastewater in Fenton process requires lower activation en-

ergy and can be easily achieved.
analysis of the raw and treated DAF manufacturing wastewater.
According to Fig. 6a, more than 20 organic compounds were iden-
3.3. Biodegradability improvement
tified in raw DAF manufacturing wastewater, and the main com-
pounds are summarized in Table 2. These compounds included
Ordinarily, when the BOD5/COD (B/C) ratio of the wastewater is
aromatic organics (72.42%), straight-chain paraffin (9.84%), alco-
higher than 0.4 it is considered to be biodegradable [33,34]. With a
hols (6.97%), and some other typical organic pollutants. Among
B/C ratio of 0.32, the raw DAF manufacturing wastewater was
these compounds, mequinol (67.88%) is toxic and bio-refractory,
clearly bio-refractory and difficult to be biodegraded by the acti-
usually affecting the performance of municipal and industrial
vated sludge process. To analyze the potential use of combined
wastewater treatment plants [36]. This phenolic compound might
chemical–biological treatments, the biodegradability of treated
be mainly responsible for the low biodegradability of the DAF man-
DAF manufacturing wastewater was monitored by measuring the
ufacturing wastewater. In comparison, the chromatogram in
B/C ratio [35].
Fig. 6b shows that the amount of most organic pollutants de-
Fig. 5 shows the COD, BOD5, TOC and B/C ratio of treated DAF
creased sharply and more than 97.0% of mequinol disappeared
wastewater with time under the optimum reaction conditions ob-
after Fenton pretreatment. According to Kang’s research [37],
tained before. As observed, a quick degradation was detected with
Fe2+ and its interaction with the organic intermediate play an
COD falling from 1091 mg/L to 580 mg/L after 2.0 h reaction, corre-
important role in improving the decomposition of phenolic com-
sponding to about 47.0% reduction. With the COD reduction, the
pounds. Therefore, the Fenton process has unique advantages to
BOD5 slightly increased from the initial 349 mg/L to the final
transform bio-refractory organic pollutants into biodegradable
400 mg/L while the B/C ratio significantly increased from 0.32 to
by-products in the pretreatment of DAF manufacturing wastewa-
0.69 after 2.0 h of Fenton reaction, which meant the treated waste-
ter. Regarding these results, the Fenton process can be considered
water was readily biodegradable. The TOC decreased from 410 mg/
as a promising process for the pretreatment of DAF manufacturing
L to 267 mg/L, indicating that about 35.0% organic carbon was fi-
wastewater prior to biological treatment.
nally mineralized in the Fenton process.
The improved biodegradability of DAF manufacturing wastewa-
ter can be explained by the removal of bio-refractory organic com- 3.4. Spectrum analysis of the wastewater
pounds in the Fenton process. This was confirmed by GC–MS
FTIR and EEM spectra have been widely used for the character-
ization of organic compounds in water or wastewater [38–45]. In
-1.0
order to gain a better insight into the transformation characteris-
tics of organic pollutants in the Fenton process, FTIR and EEM spec-
-1.5
y =-0.5005+13.84 tra were applied to the analysis of the general functional groups
2
R = 0.9202 and molecular configuration.
-2.0
Fig. 7a is the FTIR adsorption spectrum of the raw DAF manufac-
turing wastewater. A broad peak between 3400 and 3600 cm1
lnk

-2.5
may be attributed to the overlap of NAH stretching, OAH stretch-
ing and hydrogen-bonded OH of carboxylic acids in the inter- and
-3.0 intra-molecular hydrogen bonding of polymeric compounds, such
as alcohols, phenols and carboxylic acids [38]; the band at
-3.5 2965 cm1 is attributed to the stretching of CH2 group; the band
at 2250 cm1 is attributed to the stretching of C„N in fatty nitriles
-4.0 [33]; the band at 1718 cm1 is indicative of the C@O stretching
3.0 3.1 3.2 3.3 3.4 3.5 3.6
3 -1 vibration due to non-ionic carboxyl groups (ACOOH, ACOOCH3)
10 /T (K )
and may be attributed to hydrogen bonding between carboxylic
Fig. 4. Arrhenius plot of the apparent first-order kinetics constants observed for or their esters [39]. The raw wastewater was also found to have
Fenton reaction of DAF manufacturing wastewater at different initial temperature. peaks at 1640, 1410, 1050 and 1197 cm1, which are assigned to
324 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326

14.0M
12.0M (a) 4
10.0M
Abundence
8.0M 3
6.0M
7 9 10
1.5M
1.0M 13
1
5 6 8 11 12 14 15
500.0k 2
0.0
5 10 15 20 25 30 35 40 45
Retention Time (min)
14.0M
12.0M
10.0M (b)
Abundence

8.0M
6.0M
1.5M
1.0M
500.0k
0.0
5 10 15 20 25 30 35 40 45
Retention time (min)

Fig. 6. GC–MS chromatograms of: (a) raw and (b) treated DAF manufacturing wastewater by Fenton process.

Table 2
Main organic pollutants identified in DAF manufacturing wastewater by GC–MS analysis.

Retention time (min) Chemicals Similarity (%) Area (106) Removal (%)
Untreated Treated
1 5.037 N, N-dimethyl-formamide 78 27.14 – 100
2 7.084 Ethylbenzene 90 3.09 2.89 6.47
3 13.387 1-Octanol 91 95.91 – 100
4 17.874 Mequinol 95 934.02 22.12 97.63
5 19.250 E-cinnamaldehyde 97 6.52 2.43 62.73
6 22.633 Tetradecane 98 12.84 8.02 37.53
7 24.088 Dimethyl phthalate 91 32.48 – 100
8 26.792 2,6-Bis(1,1-dimethylethyl)-4-ethyl-phenol 93 4.39 2.38 45.79
9 27.496 Hexadecane 95 42.04 30.27 27.99
10 31.869 Octadecane 96 37.11 24.42 34.20
11 33.332 1,2-Benzenedicarboxylic acid, butyl 2-methylpropyl ester 80 8.79 4.08 53.58
12 35.188 Dibutyl phthalate 95 7.52 4.27 43.22
13 35.839 Eicosane 97 23.70 15.11 36.24
14 39.469 Docosane 94 12.98 8.04 38.06
15 42.810 Tetracosane 98 6.84 3.73 45.47

a -- Raw are aromatic compounds, phenolic and/or alcohol compounds and

1.0
b -- Treated some nitrogenous compounds. Fig. 7b is the FTIR adsorption spec-
trum of the treated DAF manufacturing wastewater with Fenton
process under the optimum conditions. This spectrum shows that
Transmittance / %

0.8 b most peak intensity of the treated wastewater was lower than
2345 a those of the raw wastewater. Some peaks (e.g., the peak at
2965
2250 799 2250 cm1 and the peak at 1718 cm1) nearly disappeared. These
1718 results indicated that the main pollutants, such as aromatic com-
0.6 741
528
3446 1410 995
pounds and organic nitriles, could be largely decomposed or trans-
1640
formed by the Fenton process.
616
Compared with FTIR spectra, EEM spectra provide more infor-
0.4 1050
1197
mation on the molecular configuration of organic compounds. In
order to better discriminate the fluorescence organic matters in
4000 3500 3000 2500 2000 1500 1000 500 0
-1 wastewater, excitation and emission boundaries were operation-
Wavenumber / cm
ally divided into five regions based on the results by Chen et al.
Fig. 7. FTIR spectra of: (a) raw and (b) treated DAF manufacturing wastewater. [42]. As shown in Fig. 8a, five fluorescence peaks (B1, B2, B3, T1,
and T2) were observed in the EEM spectra of the raw wastewater.
NAH bending vibration and/or C@O stretching, CAN stretching of Peak B1 was located at the Ex/Em wavelengths of 220 nm/295 nm in
amine and stretching of CAO [40]. These peaks suggested that Region I, and was related to monocyclic aromatics, such as ben-
the main organic pollutants in the DAF manufacturing wastewater zene, toluene, aniline, and phenol [43,44]. Peak B2 was detected
 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326
Fig. 8. EEM spectra of different reaction time of the Fenton process.
at the Ex/Em of 225 nm/330 nm in Region II, and peak B3 was cen-
tered at the Ex/Em of 285 nm/320 nm in Region IV. These two
intensive peaks were probably related to bicyclic aromatic com-
pounds, including ethylbenzene, naphthalene, and xylene [45].
In addition, a shoulder peak (T1) was detected at the Ex/Em of
230 nm/410 nm in Region III, and another peak (T2) was found
at the Ex/Em of 325 nm/400 nm in Region V. These two peaks
were likely due to fulvic-like compounds which contained three
to five aromatic rings, such as phenanthrene, pyrene, benzy pyr-
ene, and furan [43]. After 15 min Fenton reaction, the three peaks
(B1, B2, and B3) nearly disappeared and the fluorescence signals in
Region I, II, and IV were greatly weakened (Fig. 8b), which indi-
cated that monocyclic and bicyclic aromatic compounds were
fully decomposed by the Fenton reaction. The fluorescence inten-
sity of peak T1 significantly decreased in the first 15 min, there-
after it decreased slightly (Fig. 8c and d). However, peak T2
exhibited no obvious change during the 60 min of Fenton pro-
cess. These results indicated that most of the fluorescence com-
pounds with simple structure were broken and oxidized after
15 min of Fenton reaction, whereas the aromatic compounds
with complex structure could not be decomposed and trans-
formed during the process. Furthermore, the peak T1 and T2 were
red shifted in both excitation and emission wavelengths after
15 min of Fenton reaction. This result suggested that, although
the complicated aromatics could not be decomposed during the
Fenton process, they were oxidized by the hydroxyl radical with
the carbonyl and carboxyl groups generated in the aromatic
structure [42].
325
4. Conclusion
In this work, a parametric study was performed to evaluate the
effect of H2O2 dosage, Fe2+ dosage, initial pH value and reaction
time on the COD removal of DAF manufacturing wastewater by
the Fenton process. About 47.0% of the COD removal efficiency
was achieved under the optimum conditions: 90.0 mM hydrogen
peroxide, 20.0 mM ferrous ions, pH 3.0, and 120 min reaction time.
The kinetic study indicated that the COD degradation of DAF
manufacturing wastewater followed the pseudo first-order kinet-
ics and the apparent activation energy was determined to be
41.6 kJ mol1. After the Fenton pretreatment, the B/C ratio of the
wastewater increased from 0.32 to 0.69. The improvement of bio-
degradability may be attributed to the removal of bio-refractory
and toxic compounds from the wastewater as confirmed by GC–
MS, FTIR and EEM analyses. The Fenton process is an effective
method for the pretreatment of DAF manufacturing wastewater
prior to biological processes.
Acknowledgements
This work was supported by The National Key Scientific and
Technological Project for Water Pollution Control and Management
(2012ZX07202-002 & 2012ZX07202-005) and the Sino-French
International Scientific and Technological Cooperation Project for
Petrochemical & Pharmaceutical Industrial Water Conservation
and Pollution Reduction Cooperative Research (2010DFB90590).
326 J. Wei et al. / Chemical Engineering Journal 218 (2013) 319–326

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