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Treatment of fertilizer industry wastewater by

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catalytic peroxidation process using copper-loaded
SBA-15
a a b
Seema Singh , Vimal Chandra Srivastava & Tapas Kumar Mandal
a
Department of Chemical Engineering, Indian Institute of Technology, Roorkee,
Uttarakhand, India
b
Department of Chemistry, Indian Institute of Technology, Roorkee, Uttarakhand, India
Published online: 01 Sep 2015.

To cite this article: Seema Singh, Vimal Chandra Srivastava & Tapas Kumar Mandal (2015): Treatment of fertilizer industry
wastewater by catalytic peroxidation process using copper-loaded SBA-15, Journal of Environmental Science and Health, Part
A: Toxic/Hazardous Substances and Environmental Engineering, DOI: 10.1080/10934529.2015.1074481

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 Journal of Environmental Science and Health, Part A (2015) 0, 111
Copyright Taylor & Francis Group, LLC
ISSN: 1093-4529 (Print); 1532-4117 (Online)
DOI: 10.1080/10934529.2015.1074481

Treatment of fertilizer industry wastewater by catalytic

peroxidation process using copper-loaded SBA-15

SEEMA SINGH1, VIMAL CHANDRA SRIVASTAVA1 and TAPAS KUMAR MANDAL2

1
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Uttarakhand, India
2
Department of Chemistry, Indian Institute of Technology, Roorkee, Uttarakhand, India

The present study reports use of the catalytic peroxidation (CPO) method for treatment of actual fertilizer industry wastewater (FIW)
by using copper-loaded Santa Barbara amorphous-15 (Cu/SBA-15) catalyst. FIW consists of toxic nitrogenous and phosphorus
Journal of Environmental Science and Health, Part A

containing compounds that are not easily degraded by the conventional physicochemical and biological treatment methods. In the
present study, BoxBehnken (BB) experimental design methodology was used for optimization of three independent parameters
namely catalytic dose (m), initial pH (pHo), and H2O2 concentration. Maximum 83% COD removal was obtained at m D 4.5 g L1,
pHo D 9.2 and H2O2 concentration D 2.0 mL L1. Wastewater and catalyst recovered at optimum treatment condition were
characterized by various techniques. UV-visible and Fourier transform infrared (FTIR) techniques were used for understanding the
treatment mechanism. Textural and thermogravimetric (TGA/DTA) analysis were used for determining the characteristic of
catalyst before and after treatment. The stability and performance of the Cu/SBA-15 catalyst was also determined by using the
reusability tests.
Keywords: Catalytic per-oxidation, chemical oxygen demand, fertilizer industry wastewater, Cu/SBA-15, wastewater
characterization.

Introduction the treatment of fertilizers and pesticides containing waste-

Wastewater generated from the fertilizer industry contains
persistent, hazardous, highly toxic refractory organic com-
pounds that have a disgusting odor. Although fertilizer
industry wastewater (FIW) has low biological oxygen
demand (BOD), it has high chemical oxygen demand
(COD). Hence, it is not easily biodegradable and inhibits
growth of micro-organisms in the aquatic environment.[1]
A United Nations report noted that only a minor amount
of fertilizers are used by the crops, and rest eventually con-
taminate water and air, contributing to bioaccumulation
and public health problems.[2,3]
Numerous methods such as biological methods,[4] physio-
sorption,[5,6] incineration,[7,8] advance oxidation processes
(AOP),[9] combined oxidation with biological treatment,[10]
photo-catalytic oxidation,[1113] membrane technology,[14]
ozonation[15] and Fenton oxidation[16,17] have been used for
Address correspondence to Vimal Chandra Srivastava,
Department of Chemical Engineering, Indian Institute of
Technology Roorkee, Roorkee, Uttarakhand 247667, India;
E-mail: vimalcsr@yahoo.co.inor; vimalfch@iitr.ac.in
Received May 2, 2015.
Color versions for one or more of the gures in the article can be
found online at www.tandfonline.com/lesa.
water. The catalytic wet oxidation (CWO) technique is an
alternate AOP technique for treating refractory organic pol-
lutant wastewater in the presence of oxygen or air as an oxi-
dant.[18,19] Compared to Fenton oxidation (mild conditions
 353 K and atmospheric pressure), CWO requires higher
temperature (100300
C) and pressure (110 MPa).[20,21]
However, Fenton oxidation has some operating drawbacks
such as leaching of iron, restricted operation around pH D 3
and a huge amount of sludge generation.[22, 23]
In catalytic peroxidation (CPO), homogeneous or het-
erogeneous catalysts help in the degradation of organic
pollutants into non-toxic and harmless compounds using
hydrogen peroxide (H2O2) as an oxidant under mild condi-
tions with low energy consumption as compared to CWO.
During CPO, H2O2 generates a wide variety of free radi-
cals and other reactive species that are capable of trans-
forming or decomposing organic chemicals.[24] Figure 1
shows that a large numbers of reactive species get gener-
ated from H2O2 during the CPO process which work both
as oxidants and reductants.[25] Heterogeneous CPO sys-
tems with different transition metals loaded on various
solid support materials have been reported in
literature.[26,27]
Solid support having heterogeneous catalyst provide suf-
cient surface area for interaction of the organic pollutants
 2 Singh et al.
Journal of Environmental Science and Health, Part A
Fig. 1. Role of hydrogen peroxide during CPO of wastewater.
with active hydroxyl radicals (OH) generated by hydro-
gen peroxide for increasing the degradation efciency of
organic pollutants.[28] It is easy to recover and separate
heterogeneous catalysts from the treated wastewater.[19,24]
Copper is a cheap, easily available and most widely used
transition metal catalyst in comparison to costlier high
molecular weight transition metal catalysts such as ruthe-
nium, palladium, platinum, gold, etc.[24,26] Similarly,
ordered mesoporous silica solid support material with
well-dened pore
size (i.e., materials with pores in the
range of 20500 A) such as SBA-15 play important role in
improving the selectivity, stability and activity of catalyst
by increasing its surface properties.[29,30] SBA-15 has
hydrothermal stability, higher thermal stability, thicker
pore wall, uniform tubular mesopores and large surface
area; therefore, it acts as good catalyst support and
increases the catalytic efciency per gram of copper
catalyst.[31]
In our previous studies, catalytic oxidation of individual
nitrogenous aromatic compounds like pyridine, picoline,
etc. was reported.[19,24,26] AOPs have been used rarely for
treatment of actual FIW. To the best of the authors
knowledge, CPO treatment of FIW is being reported rst
time in the present study. Optimization of the parameters
has been done by using statistical experimental Box
Behnken (BB) design methodology. Characterization of
wastewater and catalysts has been done before and after
treatment using various sophisticated techniques. Kinetic,
leachability and reusability studies during the CPO at opti-
mum condition have also been performed and reported.
Material and methods
Chemicals and synthesis of Cu/SBA-15 catalyst
Analytical reagent (AR) grade chemicals have been used in
this study. Pluronic P123 (PEO20-PPO70-PEO20, Aldrich,
Germany), tetraethylorthosilicate (TEOS) (Aldrich, Ger-
many), copper sulfate (SD Fine Chemicals, India),
30 wt.% hydrogen peroxide (Ranken, India), HCl
(Ranken, India), etc. were purchased from various compa-
nies. Cu/SBA-15 catalyst was synthesized following a
two-step procedure as per the method reported earlier. Cu
loaded in the catalyst was 5%, which was selected as per
our previous study.[19,24]
Characterization of fertilizer wastewater
Actual FIW was obtained from a fertilizer plant in the north-
ern part of India. Various parameters of wastewater were
 Catalytic peroxidation of fertilizer industry wastewater 3

Table 1. Characteristics of fertilizer industry wastewater before Experimentation methodology

and after CPO treatment.
A round-bottomed, three-necked 250-mL glass reactor was
Parameters Before treatment After treatment used for the CPO experimental studies. This reactor was t-
ted with a total reux system at the top to minimize the evap-
COD 4982 747.43
oration of fertilizer wastewater. The ask itself was kept in
TOC 2198 667
pH 9.2 11.3 an oil bath with a magnetic stirrer, which was kept above a
Turbidity (NTU) 87 56 hot plate. The magnetic stirrer was used for agitation to
TSS (mg/L) 156 98 keep the solution homogenous during each experimental
NH3-N 113 mg/L 62.6 mg/L run. The hot plate was used to increase the temperature of
NO3-N 270 mg/L 217.5 mg/L reaction mixture at the desired level, and a proportional
TKN 180 mg/L 95.3 mg/L integralderivative (PID) controller maintained temperature
TN 450 mg/L 286.5 mg/L during the experimental runs. A 100-mL reaction mixture
TP 2.0 mg/L 0 mg/L was taken at the start of each experimental run. Cu/SBA-15
catalyst and hydrogen peroxide oxidant were added to the
reaction mixture at the desired level at zero time. pH of the
characterized as per standard method of analysis.[32] COD
solution was adjusted using 0.1 M H2SO4 and 0.1 M
measurement before and after CPO treatment was done
NaOH. A 1.0-mL sample was withdrawn at the desired time
using digestion unit (DRB 200, Hach, USA) and double
to determine the residual COD in the treated wastewater.
beam UV-Visible spectrophotometer (Hach, DR 5000,
Journal of Environmental Science and Health, Part A

All experiments were done in duplicate.

USA). Turbidity of the sample was measured by a turbidity
meter (2100P, Hach). Total organic carbon (TOC) analyzer
(TOC-V-CSN 39208967, Shimadzu) containing non-disper-
sive infrared (IR) source was used to determine the TOC of
the samples. Main characteristics of FIW before and after
treatment are summarized in Table 1.
Model fitting and statistical analyses of experimental design
Optimization of parameters for the treatment of the FIW
was done using BB experimental design methodology.
Three independent experimental variables namely cata-
lytic dose (m: 0.53.5 g L1), initiator hydrogen peroxide
(H2O2: 13 mL L1) concentration and initial pH (pHo:
913) were selected as controlling factors. Ranges of the
parameters were chosen based on the conditions reported
in our previous study.[19,24] Parameters catalytic dose, initi-
ator concentration and initial pH are represented as X1, X2
and X3, respectively. Response COD removal (%) is
denoted as Y. Table 2 shows the experimental range and
levels used in this study. Full experimental plan and the
actual values used in experiments along with COD
removal efciencies (taken as response) are given in the
Table 3. A total of 17 experiments were done using the
experiment design. Experiments were done in a random
order to nullify the effect of uncontrolled factors.
For reusability study, CPO experiments were carried out
in several cycles at optimum conditions using the same cat-
alyst. Catalyst was separated from the treated solution
using a centrifuge after each cycle to recover the catalyst,
which was used again in the next cycle after drying. Dried
catalyst after the sixth cycle was characterized to deter-
mine its thermal and structural characteristics. Leaching
of Cu from catalyst at optimum condition for CPO of
FIW degradation was investigated by determining the Cu
concentration in the wastewater by inductively coupled
plasma mass spectroscopy (ICPMS: Perkin Elmer ELAN
DRC-e) after each cycle.
Instrumental and analytical methods
A UVvisible spectrophotometer (Shimadzu UV-2450) was
used to understand the changes in wavelength corresponding
to maximum absorbance (max) before and during the treat-
ment at different time intervals. A Thermo Nicolet Fourier
transform infrared (FTIR) analyzer (Magna 760) was used
(over a spectral wave number range of 4000400 cm1)
with pellets (pressed-disk) technique) to determine the
changes in functional groups in the solution with time during
the treatment. Cu/SBA-15 catalyst was collected after the
end of the CPO experiment and dried at 120
C for 6 h to
remove excess water. Thermogravimetric analysis was done

Table 2. Experimental factors their and levels.

Factors Levels

Variables Units Symbol X Low (1) High (C1)

Catalyst dose g/L (m) X1 0.5 3.5
Initial pH pHo X2 9 13
H2O2 concentration mL/L Ci X3 1 3
 4 Singh et al.

Table 3. Experimental and predicted value of response Y (COD) removal during CPO method.
COD removal (%)

Std. order Run Catalytic dose (m) (g/L)(X1) pH (pHo)(X2) H2O2 Con. (mL/L)(X3) Yactual (%) Ypredicted (%)
1 16 0.5 9 2 36 34.9
2 10 3.5 9 2 73 71.4
3 1 0.5 13 2 38 39.6
4 15 3.5 13 2 58 59.1
5 7 0.5 11 1 33 33.9
6 8 3.5 11 1 56 57.4
7 6 0.5 11 3 35 33.6
8 13 3.5 11 3 67 66.1
9 9 2 9 1 39 39.3
10 5 2 13 1 39 36.5
11 12 2 9 3 42 44.5
12 3 2 13 3 40 39.8
13 2 2 11 2 44 44.8
14 4 2 11 2 45 44.8
15 14 2 11 2 46 44.8
Journal of Environmental Science and Health, Part A

16 17 2 11 2 43 44.8
17 11 2 11 2 46 44.8

using a TGA analyzer (SII 6300 Exstar). It was used in the
temperature range of 301000
C at a heating rate of 10
C
min1 in air atmosphere with air ow rate of 200 mL min1
to identify the changes in thermal stability of the catalyst.
Mineralization efciency of FIW was estimated by the differ-
ence between the initial and nal COD.
Results and discussion
Statistical analysis
Figures 2a and b show the probability distribution plot
of residuals and the parity plot between the model pre-
dicted and experimental values. R-Squared (R2) and
adjusted R-squared values for Y response were found to
be 0.983 and 0.963 (Table A2). P-value of the lack of t
( D 0.0759) was found to be greater than 0.05 indicating
that the model could be tted to the real surface. ANOVA
result showed F-value of 47.7. A higher F-value and a
lower P-value indicate that the quadratic model repre-
sented the experimental data satisfactorily.[3336]

COD removal efciencies obtained in all experiments are

given in Table 3. Adequacy of various types of models for
representing the response was tested in terms of sequen-
tial model sum of squares, lack of t and model sum-
mary statistics, and the results are given in Table A1.
Results suggest that the cubic model was aliased, meaning
estimates of cubic model coefcients are not unique and
therefore the developed surface plots may be misleading.
The p-values and other parameters show that the qua-
dratic model seems to satisfactorily represent the experi-
mental COD removal efciencies.
Analysis of variance (ANOVA) values along with statis-
tical Fishers test values and the coefcient of determina-
tion (R2) values for quadratic model for COD removal are
shown in Table A2. The quadratic equation in terms of
coded factors for COD removal is given as:
Y% COD removal D 44:8 C 14 X1  1:875 X2 C 2:125 X3
C 7:1 X1 2  0:65 X2 2  4:15 X3 2
 4:25 X1 X2 C 2:25 X1 X3  0:5 X2 X3
(1)
Effects of variables on COD removal efficiency
Figure 3 shows the three-dimensional response surfaces (3-
D) and their corresponding contour plots for examining
the effects of the experimental variables on the response
(COD removal). Effect of pH (913) and H2O2 concentra-
tion (13 mL L1) on the COD removal (while the catalyst
dose was kept at the central level) is shown in Figure 3a
and 3b. It shows that pH has a marginal effect on COD
removal compared to H2O2 concentration. It is known
that nitrogenous compounds get protonated in the acidic
pH range and get deprotonated (neutral form) at higher
pH. Therefore, most of compounds present in FIW in the
pH range of 913 are in neutral form. Considering this,
pH has marginal effect on treatment of FIW during CPO
by Cu-SBA-15.[19,24] As the original pH of the FIW was
9.2, it was therefore taken as optimum.
H2O2 concentration was found to signicantly affect the
COD removal efciency. Radicals such as hydroxyl radi-
cal (OH), hydroperoxyl radical (HOO), superoxide radi-
cal (O2) and other oxidants such as oxygen (O2), HO2,
 Catalytic peroxidation of fertilizer industry wastewater 5

Fig. 2. (a) Probability distribution plot of residuals, and (b) relationship between the actual and predicted values of the COD removal
during CPO treatment of fertilizer industry wastewater.

and OH (hydroxyl ion) are generated during the H2O2 degradation.[37] Various types of reactive species with differ-
Journal of Environmental Science and Health, Part A

decomposition reaction during the CPO process (Fig. 1). ent potentials (as described in Fig. 1) react with the active
Figure 4 shows the reduction of the Cu catalyst and OH phase of transition metal (Cu) ion using various paths
contribution during the CPO process for FIW (Fig. 4). Two valences of Cu (Cu2C/CuC) help in generation

Fig. 3. Effect of various parameters on COD degradation during CPO treatment of fertilizer industry wastewater. (a) 3-dimensional
response surface, and (b) 2-dimensional contour plot for the effect of H2O2 and pH; and (c) 3-dimensional response surface, and (d)
2-dimensional contour plot for the effect of H2O2 and catalyst dose.
 6 Singh et al.

Fig. 4. Schematic representation of the H2O2 reaction on the sur-
face of Cu/SBA-15 catalyst.
Journal of Environmental Science and Health, Part A
Fig. 5. Variation of COD removal with time at various catalysts
dose during CPO treatment of fertilizer industry wastewater.
Actual experimental data represented by points whereas data
predicted by rst-order kinetic model represented by lines.

of various oxidation species. CuC ions are directly involved

in generation of hydroxyl radicals (steps 3 and 4). Exchange-
able sites of porous materials (SBA-15) help in stabilizing Optimum condition
the reduced oxidation states of the Cu metals.
The quadratic model given by Eq. (1) was used to deter-
COD removal increased with an increase in H2O2 con-
mine the optimum conditions for treatment of FIW by
centration. This is because the number of radicals pro-
CPO method using Cu/SBA-15 catalyst. Catalyst dose
duced during the treatment directly depends upon H2O2
was found to be the most signicant factor, and the COD
concentration.[3844] H2O2 itself acts as a powerful oxidant
removal continuously increased with an increase in cata-
and produces a sufcient amount of radicals for interact-
lysts dose (Fig. 5). Therefore, more experiments were car-
ing with the organic and inorganic impurities of the FIW.
ried out at other optimum conditions (pH D 9.2 and H2O2
However, higher H2O2 concentration decreased the COD
concentration D 2.0 mL L1) to further optimize the cata-
removal (Fig. 3c and 3d). Excess metal loaded on the sup-
lyst dose. Variation of COD removal efciency with time
port converts the active species into nascent oxygen and
is shown in Figure 5 for the catalyst dose varying in the
an excess amount of H2O2 also inhibit the chain propaga-
range from 3.5 to 5.0 g L1. It may be seen that the
tion reaction of HO radicals via the formation of
removal increased up to a catalyst dose of 4.5 g L1, after
H2O.[26,45] After the optimum H2O2 concentration, excess
which increase in COD removal was marginal. Thus, over-
H2O2 acts as a OH scavenger having higher oxidation
all optimum condition was catalyst dose D 4.5 g L1, pH
potential and reactivity as compared to hydroperoxyl radi-
D 9.2, H2O2 concentration D 2.0 mL L1 and time D 6 h,
cal (HOO), which only contributes in the oxidative reac-
which gave maximum COD removal efciency of 82%.
tion at higher H2O2 concentration.[42,43]

Kinetic study
C  OH Kinetics of the FIW treatment by CPO method with vary-
H2 O2 C  OH ! HOO ! O2 C H2 O (2) ing catalyst dose was investigated using the rst-order
H2 O
kinetic rate expression, which is given as:

 
CODo
The 3-D and contour plots in Figure 3c and d indicate ln D kt (3)
CODt
the effect of H2O2 concentration and catalyst dose on the
COD removal efciency. ANOVA results for COD
removal (Y) shows that the catalyst dose is the most signif- where k is the rate constant. Slope of lnCODo /CODt with
icant factor for the present study (Table A1). COD t gives the reaction rate constant. It may be seen in
removal efciency continuously increased with increase in Figure A1 that the data of COD removal from FIW fol-
catalyst dose from 0.50 to 3.5 g L1. At higher catalyst lowed the rst-order kinetics. R2 values > 0.94 were
dose, higher effective catalyst surface area and active sites observed for all catalysts dose studied. For catalyst doses
allow for easy degradation of pollutants in FIW. of 3.5, 4.0, 4.5 and 5.0 g L1, values of k were found to be:
 Catalytic peroxidation of fertilizer industry wastewater 7

cycle. In India, the permissible value of Cu concentration in

the discharged wastewater is 3 mg L1.[46] However, Cu
leaching in each cycle was always less than 210 mg L1,
which is much well below the permissible limit.

Spectroscopic analysis
Figure 7a represents the UVvisible spectroscopic analysis
(within the range of 200800 nm) of the wastewater after
different treatment time during the CPO treatment. Value of
the max shifted towards the lower (190 nm) during the
treatment process at optimum conditions indicating absence
of auxochrome groups. Peaks at lower max 209 and
190 nm indicate the presence of monoaromatic rings in the
solution after 4 h of treatment. Shift of the larger spectral
peaks towards the shorter wavelength called a hypsochro-
mic shift is due to the degradation of these auxochromic
Journal of Environmental Science and Health, Part A

groups.[47] Change in solvatochromic parameters such as

solvent polarity may also be responsible for this shift.

Fig. 6. (a) Catalyst reusability and treatment proles; and (b)

leaching study of Cu/SBA-15 during six cycles of CPO treatment
for fertilizer industry wastewater (Cu/SBA-15 dose D 4.5 g L1,
H2O2 D 2.0 mg L1, pHo D 9, time D 6 h).

0.18, 0.22, 0.24 and 0.26 h1, respectively. First-order

model t is shown in Figure 5.

Reusability and leaching of Cu/SBA-15 catalyst

To determine the reusability and stability of the Cu/SBA-
15 catalyst, the CPO process was repeated for six runs.
Figure 6a shows the COD degradation proles for six suc-
cessive catalytic cycles. In every cycle, COD degradation in
the range of 6883% was observed in 6 h of CPO treatment.
COD removal decreased after each cycle, and approxi-
mately 68% COD removal was observed after six cycles.
ICPMS analysis was used for determining the Cu leaching Fig. 7. (a) UVVisible, and (b) FTIR analysis of fertilizer indus-
during each of the ve cycles (Fig. 6b). Decrease in the try wastewater with time at optimum conditions (Cu/SBA-15
COD removal efciency is due to the Cu leaching in each dose D 4.5 g L1, H2O2 D 2.0 mg L1, pHo D 9, time D 6 h).
 8 Singh et al.

Figure 7b illustrates the change in functional groups

present in the FIW during the treatment. This FTIR
analysis provides information regarding the partial
destruction of compounds present in FIW during the
CPO method. Peaks at 35603450 cm1 indicate the
presence of O-H or N-H stretching frequency due to
the hydroxyl and amino groups containing organic pol-
lutants in the wastewater. Strong peaks observed at
16841664 and 1589 cm1 show concentration of aro-
matic rings containing organic derivatives in the waste-
water. After 4 h of treatment, the concentration of
aromatic derivatives containing compounds decreases.
Some new peaks get generated at 2462 and 1134 cm1,
indicating that the degradation of bigger compounds
leads to formation of smaller compounds containing
CDC and carbonyl groups.[48] At the end of the
treatment, the stretching frequency of carbonyl group
shifts towards the ngerprint region. It may be due to
Journal of Environmental Science and Health, Part A

the conversion of the carbonyl groups and mineraliza-

tion of the aromatic derivatives.

Characterization of catalyst after treatment

Thermogravimetric analysis of catalyst after treatment is
shown in Figure 7. The carbonaceous deposits on the sur-
face of the catalyst are frequently attributed to catalyst
deactivations.[36,49] Figure 8a illustrates the deposition of
the carbonaceous substances on the surface of catalyst as
identied by the TGA and DTA analysis. The weight loss
rapidly increased with increase in temperature from 250 to
450
C. Maximum weight loss occurred at 310
C due to
maximum carbonaceous materials burn off at this temper-
ature. Figure 6a shows that 2.3% weight loss occurred
because of the accumulation of the carbonaceous materials
on the surface of used catalysts. Reusability analysis indi-
cated that the COD removal efciency decreased with
each cycle. It may be due to the deposition of carbona-
ceous and nitrogenous substances on the surface of the cat-
alyst after each cycle. However, DTA analysis conrmed
that the impurities deposited on the surface of the catalyst
could be oxidized at about 310
C.
Textural properties of Cu/SBA-15 catalyst before and
after treatment were determined using the nitrogen adsorp-
tiondesorption measurements (Fig. 8b). It was found that
the catalyst exhibited the same type IV-isotherms before and
after treatment. In both cases, structures have H2 type hyster-
esis loop, which is due to the presence of ink-bottle pores in
the catalyst.[50] In the case of used catalyst, the height of the
hysteresis loop shows a small decrease, causing a decrease in
surface area compared to virgin catalyst. Figure 8c shows the
changes in the distribution of surface area and pore volume
of the catalyst before and after the treatment. BET surface Fig. 8. (a) TGA analysis, (b) nitrogen adsorption (A)desorption
area of the catalyst decreased from 607 to 571 m2 g; 1 pore (D) isotherms, and (c) pore area and pore volume distribution of
volume decreased from 0.7 to 0.66 cm3 g1 and pore Cu/SBA-15 catalyst before and after treatment.
 Catalytic peroxidation of fertilizer industry wastewater


diameter decreased from 46.6 to 45.8 A after its usage in the
CPO process.[51] Decrease in the textural properties indicate
deposition of some material on the surface of catalysts.
Conclusion
In present study, treatment of FIW was studied by a CPO
process using copper-loaded SBA-15 catalysts. BB experi-
mental design was used to optimize operating parameters.
COD removal efciency of 83% was observed at the opti-
mum condition of catalyst dose D 4.5 g L1, H2O2 con-
centration D 2.0 mL L1 and pH D 9.2. UV-visible and
FTIR analysis of wastewater during the treatment con-
rmed oxidation of compounds present in the fertilizer
during the CPO process. Recycle test results, and low Cu
leaching conrmed good operational stability of the Cu-
loaded SBA-15 during the CPO. Pore area analysis of the
catalyst before and after treatment showed some deposi-
Journal of Environmental Science and Health, Part A
tion of materials on the catalysts surface; however, TGA
analysis conrmed that after heating the catalyst at 350
450
C, it can be further reused for the CPO process.
Funding
The authors are thankful to Department of Science and
Technology (DST), India for providing nancial help for car-
rying out this work under its Water Technology Initiative
(WTI) program (Grant no. DST/TM/WTI/2k13/127).
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Appendix
Table A1. Adequacy of the model tested using sequential model sum of squares, lack of t tests and model summary statistics
for COD removal of fertilizer industry wasewater treatment during CPO.
Sequential model sum of squares
Source Sum of squares Degree of freedom Mean square F value Prob > F Remark

Sequential model sum of squares

Mean 35788.2 1 35788.2
Linear 1632.2 3 544.1 17.7 <0.0001
2FI 93.5 3 31.1 1.01 0.4249
Quadratic 273.4 3 91.1 19.6 0.0009 Suggested
Cubic 25.7 3 8.5 5.04 0.0759 Aliased
Residual 6.8 4 1.7
Total 37820 17 2224.71
Lack of t tests
Liner 392.7 9 43.6 25.66 0.0034
2FI 299.2 6 49.8 29.33 0.0029
Quadratic 25.7 3 8.58 5.04 0.0759 Suggested
Cubic 0 0 Aliased
Pure Error 6.8 4 1.7
(continued on next page)
 Catalytic peroxidation of fertilizer industry wastewater 11

Table A1. Adequacy of the model tested using sequential model sum of squares, lack of t tests and model summary statistics
for COD removal of fertilizer industry wasewater treatment during CPO. (Continued)
Model summary statistics
Source Standard deviation R-Squared Adjusted R-Squared Predicted R-Squared PRESS Remark

Linear 5.56 0.803 0.757 0.594 824.07

2FI 5.53 0.849 0.759 0.251 1521.49
Quadratic 2.15 0.983 0.963 0.791 422.62 Suggested
Cubic 1.30 0.996 0.986 Aliased

Table A2. Results of regression analysis of the second-order polynomial model for optimization of COD removal of fertilizer industry
wasewater treatment during CPO.
Source Coefcient estimate Sum of squares Degree of freedom Mean square F-value Prob > F Remark
Model 1999.215 9 222.135 47.77 <0.0001 Signicant
Intercept 44.8
X1 17.38 1568 1 1568 337.20 <0.0001
Journal of Environmental Science and Health, Part A

X2 2.63 28.125 1 28.12 6.04 0.0435

X3 3.25 36.125 1 36.12 7.76 0.0270
X12 6.60 212.2526 1 212.25 45.64 0.0003
X22 3.40 1.778947 1 1.77 0.38 0.5558
X32 7.15 72.51579 1 72.51 15.59 0.0055
X1X2 0.00 72.25 1 72.25 15.56 0.0056
X1X3 0.75 20.25 1 20.25 4.35 0.0753
X2X3 1.75 1 1 1 0.21 0.6569
Residual 32.55 7 4.65
Lack of t 25.75 3 8.58 5.04 0.0759 Not signicant
R2 0.983
R2adj 0.963

Fig. A1. First-order [ln(CODo/CODf) versus time] plot.