Chemical Engineering Journal 210 (2012) 33–44

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Chemical Engineering Journal

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Response surface-optimized Fenton’s pre-treatment for chemical precipitation

of struvite and recycling of water through downstream nanofiltration
Ramesh Kumar, Parimal Pal ⇑
Environment and Membrane Technology Laboratory, Chemical Engineering Department, National Institute of Technology, Durgapur 713 209, India

h i g h l i g h t s

" Optimization of Fenton’s process done by response surface methodology (RSM).

" 98% recovery of ammonia as struvite fertilizer achieved in chemical precipitation.
" Integration of flat sheet cross flow membrane modules turned water reusable.
" Novel approach produced struvite free from cyanide and phenol contamination.

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

Article history: Experimental investigations were carried out on a new membrane-integrated hybrid treatment scheme
Received 21 May 2012 for removal of hazardous cyanide and phenol from coke wastewater and chemical precipitation of ammo-
Received in revised form 8 August 2012 nia as a value-added struvite by-product. Fenton’s pre-treatment with response surface optimization
Accepted 14 August 2012
ensured very effective removal of cyanide and phenol facilitating subsequent chemical precipitation of
Available online 28 August 2012
over 98% ammonia as pure struvite fertilizer. Integration of micro and nano-membrane filtration with
these chemical treatment units raised water quality to reusable level. Largely fouling-free flat sheet cross
Keywords:
flow membrane modules could remove over 96–98% of the chemical contaminants while still yielding a
Chemical precipitation
Response surface optimization
high flux of 116 l/h/sq m of the membrane surface at a transmembrane pressure of only 15–16 bars. The
Struvite recovery new integrated scheme embracing the concept of zero emission and value addition is a novel approach in
Recycling continuous treatment of industrial wastewater for recycling.
Zero emission Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction generated, biological treatments like activated sludge process, nitri-

In the iron and steel making industries around the world, mil-
lions of tonnes of metallurgical coke are used in the blast furnace
and the coke plants produce this coke by carbonization of coal. After
carbonization, enormous quantity of water is used for quenching
the hot coke mass and for washing the coke-oven gases. Liquid efflu-
ents thus generated during coke making are heavily polluted with
cyanide, phenol, ammonia and varieties of other organic as well as
inorganic pollutants that can be broadly expressed in terms of
COD (Chemical Oxygen Demand) and BOD (Biochemical Oxygen
Demand). This wastewater on being discharged from industry
pollutes hundreds of kilometer of river bodies affecting both aquatic
lives and human health seriously. Effective treatment of coke
wastewater has for long remained a challenge to the scientific
community. Considering the enormous quantity of the wastewater
⇑ Corresponding author. Tel.: +91 343 2755055, mobile: +91 9434469750; fax:
+91 343 2754078.
E-mail addresses: parimalpal2000@yahoo.com, parimalpaul1999@yahoo.in
(P. Pal).
fication, denitrification and similar treatments are often considered
as low cost options. But high concentration of certain pollutants like
cyanide and phenol often leads to failure of biological treatment
plants [1]. Though individual biodegradation of phenol, cyanide
(CN), thiocyanate (SCN) and ammonia–nitrogen (NHþ 4  N) has
been found to be effective, their combined presence in a wastewater
stream, however, turns successful treatment a difficult task [2,3].
Metal-complexes like ferricyanide are very difficult to degrade
through biological methods, so it remains in the effluent [4].
Conventional methods like caustic chlorine treatment can convert
cyanide into cyanate but this is also toxic. Moreover, chlorination
also produces secondary by-products such as trihalomethanes and
chloro-phenols, which are highly toxic and suspected carcinogens
and are also less effective for the removal of iron cyanide [5].
Simultaneous presence of phenol and cyanide opposes each other’s
removal [6]. The other physico-chemical processes that have been
studied include stripping of ammonia after removal of cyanide
and phenol. But this adds to air pollution and is often expensive
due to involvement of chemical feed, stripping tower, pump and

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.08.036
34 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44
Nomenclature
Jw the pure water permeability
DP the difference in applied pressure across the membrane
rp pore radius
d the thickness of the membrane
l viscosity of fluid
Cis feed side concentration of solute
Cip permeate side concentration of solute
Ji solute flux i
Di diffusivity of solute i
ci the concentration of solute i at the surface of the mem-
brane
x mole fraction for solute i
zi the valance of solute i
liquid spray system, forced air and carbonization system [7]. Ad-
vanced oxidation processes (AOPs) using ultraviolet (UV) radiation
in combination with various oxidants (viz. Fenton’s reagent) have
also been used for the treatment of effluents containing toxic com-
pounds like cyanide, phenol, etc. which are refractory in nature and
difficult to be oxidized completely by conventional methods [8]. Ul-
tra-violet radiation (UV), Ozone (O3), hydrogen peroxide (H2O2) and
their various combinations as well as photo-Fenton methods [9]
broadly fall in the category of advanced oxidation process. However,
the major drawbacks of the AOPs are the high cost of the chemical
reagents and expenses on operation and maintenance of special
light sources such as ultra-violet lamps [10]. In the recent years,
membrane-integrated approaches have been adopted for treatment
of industrial wastewater to achieve high quality of effluent [11,12].
Though biological treatment plants have most widely been stud-
ied and practised in handling coke wastewater, such plants often
fail due to inadequate attention that largely result from non-reve-
nue activities in waste treatment plants. Thus, in the present article,
a novel approach has been adopted to address these issues. The first
and the most important step is the optimization of Fenton’s meth-
od. In conventional optimization study, effect of one governing
parameter on the response of interest is normally found out keep-
ing other parameters constant. But in a real situation, there may
be mutual interactions of the control variables and such interac-
tions cannot be taken care of in conventional optimization study.
Response surface methodology is an experimental strategy that
develops a fairly realistic functional relationship between the re-
sponse of interest and the controlling or governing variables
through empirical statistical modeling. It takes care of mutual inter-
actions of the variables through introduction of the interaction
terms in the developed model. Though other approaches are also
there for process optimization, there are always limitations of each
approach in matters of involvement of controlling variables, num-
ber of experiments, practical difficulty of conducting extremely
large number of experiments, probability of introduction of large
errors through inadequate number of experiments, etc. Considering
the number of variables involved and region of response in the
present investigation, the response surface optimization approach
of Design Expert Software (Design-ExpertÒ Version 8.0.6) was used
in the experimental strategy. The conventional technique for the
optimization of multivariate system usually defines one factor at
a time. RSM is very useful for developing, improving and optimizing
processes by utilizing its mathematical and statistical tools [13]. It
has unique ability to generate the relationships between the re-
sponse and the independent variables with a minimum number
of trials according to special experimental design. Moreover, RSM
is less expensive and faster than the classical methods [14]. In clas-
sical factorial design, range of a parameter (upper limit and lower
F Faraday’s constant
R the gas constant
T temperature
W the electric potential
Ki the distribution coefficient of solute i
Jv the volume flux and can be estimated based on the
membrane area
Ci the bulk (or feed) concentration of solute i
WD Donnan potential
Ws electrical potential of the solution
Wm electrical potential of the membrane
Ci initial concentration of the pollutants
Cf residual concentration in the permeate side
limit) cannot be determined, but in RSM with the help of central
composite design a fixed range can be taken. It is very difficult in
case of classical factorial design to develop a mathematical equa-
tion for interaction of parameters which is possible in case of
RSM. RSM can provide optimized value in less number of experi-
ments for large number of variable parameters which is not possi-
ble in case of classical factorial optimization. Quite a few studies
[15–17] have attempted to recover nutrients in the form of struvite
(magnesium ammonium phosphate) from wastewater in order to
add economy to the process. But in most of these cases, studies
were on municipal wastewater or poultry wastewater and were lar-
gely in batch mode. Coke wastewater containing so many hazard-
ous pollutants has not received adequate attention in this
context. In complex steel making industry, a treatment plant of
coke wastewater often fails to attract desired attention as it does
not directly produce any product and the conventional treatment
steps are time-consuming. In this fast changing world, there is ‘no
time for waste’ and hardly the existing treatment schemes are in
tune with the ‘zero emission’ concept. Thus there needs to be inno-
vative approaches in turning waste treatment plants economically
attractive, technologically innovative and operationally interesting
with incorporation of ‘zero emission’ concept and value addition to
chemical compounds present as pollutant. The present integrated
treatment scheme is an attempt in simultaneously turning waste-
water reusable while converting chemical pollutant into value-
added product. Such a scheme is expected to result in zero emission
and enhanced economic viability towards sustainable management
of water resource.
2. Theoretical
Cyanide and phenol can be degraded by chemical method (Fen-
ton’s reagent) and ammonia may be precipitated out by addition of
magnesium and phosphate salts. The principle of the Fenton’s pro-
cess is the catalytic cycle of the reaction between iron (catalyst)
and hydrogen peroxide (oxidant) to produce hydroxyl radicals
[18]. Hydrogen peroxide is used in broad spectrum for the chemi-
cal oxidation of the dissolved organic and inorganic compounds
present in the industrial effluents as H2O2 is strong oxidizing agent
(oxidation potential 1.77). The hydroxyl radical (OH) can destroy
structure of organic synthesis because of strong oxidation. Hydro-
gen peroxide is a very weak acid and liberates molecular oxygen in
the presence of trace alkali. Iron acts as a catalyst and its addition
results in a positive impact on the removal of pollutants. However,
increasing the iron concentration may also increase downstream
problems associated with the metal’s removal. Fenton’s treatment
has two distinct stages [19] namely Fenton’s oxidation (OH
generation) and Fenton’s coagulation. Ferric coagulation following
 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44 35

oxidation results into sludge. OH radical generation in Fenton’s Ionic transport through nanofiltration membranes has widely
treatment takes place following the reaction below: been explained by models based on Donnan equilibrium theory
that states the equality of electrochemical potential (W) of the
H2 O2 þ Fe2þ ! Fe3þ þ OH þ OH ð1Þ solutions on either side of the solution–membrane interface. The
2+ concentration at the surface of the membrane can be estimated
There is a possibility of auto regeneration of Fe in this system
that acts as catalyst. using the Donnan equilibrium as shown in the following equation:
 
Feþ3 þ H2 O2 ! HO2 þ Feþ2 þ Hþ ð2Þ F
WD ¼ Wm  Ws or C i ¼ C i exp zi WD ð10Þ
RT
Dosing of the hydrogen peroxide concentration results in the in-
creased availability of the hydroxyl radicals (OH) in the solution
where Ci is the bulk (or feed) concentration of solute i; Donnan po-
increasing the rate of oxidation of cyanide compound which is first
tential (WD) is the difference between the electrical potential of the
oxidized to cyanate and then further oxidized to ammonium and
solution (Ws) and the electrical potential of the membrane (Wm).
carbonate ions through the reactions below:
The Nernst-plank equation coupled with the Donnan Equilibrium
CN þ H2 O2 ! CNO þ H2 O ð3Þ has been shown to accurately predict the rejection of various salts
by nanofiltration and reverse osmosis membrane [23,24]. Eqs.
H2 O2
CNO þ 2H2 O ! NHþ4 þ CO2
3 ð4Þ (10) and (11) show that solute concentrations at the surface of
Phenol can be degraded following the reaction with hydrogen per- the membrane as well as charge on the membrane surface deter-
oxide in the presence of iron as a catalyst as below: mine retention or passage of the solutes. If the ion is neutrally
charged, then the concentration at the membrane surface is unaf-
C6 H6 O þ 14H2 O2 ! 6CO2 þ 17H2 O ð5Þ fected by the charge of the membrane [23,24] and separation lar-
Phenol oxidation produces cyclic intermediates hydroquinone gely follows steric mechanism.
(HQ), and catechol (CTL) and a strong brown color is obtained in At pH values greater than 7.0 most of the polyamide composite
presence of H2O2 that could be due to quinine condensation [20]. nanofiltration membranes possess negative zeta potential [25].
This ammoniacal nitrogen was removed by chemical precipita- Due to the charged nature of the NF membrane, solutes with an
tion as magnesium ammonium phosphate (MAP) well known as opposite charge compared to the membrane (counter-ions) are at-
struvite. MAP is a white crystal substance consisting of equal molar tracted, while solutes with a similar charge (co-ions) are repelled.
concentrations of magnesium, ammonium and phosphorus. MAP
precipitation takes place following the chemical reaction is ex-
3. Experimental
pressed in the following equation:
Mgþ2 þ NHþ4 þ PO3
4 þ 6H2 O () MgNH4 PO4  6H2 O #; 3.1. Raw wastewater and characterization
pK s ¼ 12:6 ð6Þ
Nanofiltration membranes are in between ultrafiltration and re- Raw wastewater (influent) used in the experiments was col-
verse osmosis membranes in separation performance that can be lected from a coke oven plant (Durgapur Projects Limited, India).
predicted in terms of pure water flux and solute flux which are Table 1 presents the range and their mean value of major parame-
uncoupled. Separation of the solutes from the solution depends ters of this wastewater.
both on steric (sieving) mechanism as well as Donnan (electro-
static) exclusion principle [21] mechanisms. The steric mechanism 3.2. Materials
may be explained by continuum hydrodynamic models of Ferry
[22] whereas Donnan mechanism is well explained by extended All the chemical reagents like hydrogen peroxide, ferrous sul-
Nernst–Planck model. fate, magnesium chloride, sodium biphosphate, hydrogen chloride,
The pure water flux may be related to pressure using the sodium hydroxide, cyanide standard solution (1000 mg/L), Metha-
Hagen–Poiseuille equation, as shown in (Eq. (8)) [23]. nol (Sigma–Aldrich, WI, USA) for calibrating phenyl column and
r2p Dp phenol standard (Merck) were from Merck (Germany). All working
Jv ¼ ð7Þ solutions of required concentration were prepared using deionised
8ld
water from Milli-Q purification system (Waters, MA, USA). Thin
According to Eq. (8), increasing the pressure will increase the film composite polyamide nanofiltration (NF1, NF2, NF3, NF20)
pure water flux, while the solute flux is proportionally related to as well as poly vinylidene fluoride (PVDF) microfiltration mem-
the solute concentration gradient across the membrane. In com- branes were procured from Sepromembranes Inc. and Membrane
puting effective pressure difference between two sides of the solution (USA) respectively. The polyamide composite nanofiltra-
membrane, osmotic pressure may be taken care of using Van’t Hoff tion membranes of 165 lm thicknesses were all very effective in
equation Eq. (9). rejection of bivalent salts while having poor retention for sodium
X
Dp ¼ RT ðC is  C ip Þ ð8Þ
Table 1
where Cis, Cip are, respectively feed and permeate side concentra- Characteristics of industrial wastewater (coke-oven).
tions of the solute.
Parameter Concentration range (mg/L) Mean value (mg/L)
Solute flux is defined using in the extended Nernst–Planck
equation as shown in the following equation: Cyanide 110–138 124
    Phenol 122–202 162
dci F dw Ammonia 1720–2160 1940
J w ¼ ½K i ci J v   Di  D i zi c i ð9Þ
dx RT dx COD 3436–4276 3856
TDS 20078–28162 24120
The above extended Nernst–Planck equation describes the flux Conductivity (mS/cm) 16.06–22.18 19.12
which is the sum of the fluxes due to convection, diffusion (as a Salinity 8.35–15.05 11.7
Oil and grease 40.5–61.5 51
function of concentration gradient across the membrane) and elec-
pH 8.5–9.5 9.0
tromigration (as a function of electrical charge gradient).
36 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44

chloride as per manufacturers’ data and detail characteristics pre-
sented in Table 2.
3.3. Experimental set-up
The experimental set-up as shown in Fig. 1 consists of a 30 l
capacity continuous stirred tank reactor (CSTR) for Fenton’s treat-
ment, a 30 l capacity CSTR for precipitation of MAP (Magnesium
Ammonium Phosphate), flat sheet cross flow microfiltration and
nanofiltration membrane modules and circulation pumps along
with flow meters and pressure gauges. A circulation bath with
temperature controller (PolyScience, USA) was attached to the feed
tank to maintain constant temperature. The effective filtration area
of each membrane module was100 cm2.
3.4. Experimental procedure
3.4.1. Response surface optimization and continuous mode treatment
Fenton’s process for cyanide and phenol removal was optimized
through rigorous experimentation using response surface method-
ology (RSM) of Design Expert software (Design-ExpertÒ Version
8.0.6; serial 9 l no 7020–7114, State-ease, Inc.) and the optimum
concentrations for the reagents (FeSO47H2O and H2O2) and the
optimum pH were determined. There is hardly any reported study
on the optimization of this process specifically on simultaneous
degradation of phenol and cyanide. RSM is a statistical method that
uses experimental data generated from specific experimental de-
sign to model and optimizes any process in which several variables
influence the desired response [13]. Three major steps are involved
in optimization viz., performing the statistical designed experi-
ments, estimating the coefficients in a mathematical model and
predicting the responses and examining the adequacy of the model
[26]. RSM helps to enumerate the relationships between output
variables called responses (Y) and input variables called factors
(Xis) [13].
RSM design called Central Composite Design (CCD) was applied
in this study. It is suitable for fitting a quadratic surface and it helps
to optimize the effective parameters with a minimum number of
experiments, as well as to analyze the interaction between param-
eters [27]. Generally, the CCD consists of a 2k, 2 k and kc factorial
runs, axial runs and central run respectively [27]. The central point
helps to evaluate the experimental errors and reproducibility of
the data. Total number of experiments with different combinations
of three variables (concentrations of iron salt in the range 1.00–
3.75 g/L, hydrogen peroxide in the 1.50–5.50 g/L range and pH
3.0–10.0) was 20 (2k + 2k + kc), where k denoted the number of
variables and kc (=6), the number of central points for a three
variables system. Degradation experiments were carried out batch-
wise in 250 ml conical flasks with a working volume 100 ml in
each case in incubator shaker (speed 160 rpm) at ambient
temperature for duration of 1 h. Investigations on degradation of
phenol and cyanide following Fenton’s process were done in con-
tinuous system subsequently with the optimized parameters. The
pH of the treatment medium was adjusted by addition of sulfuric
acid (H2SO4, 2 M) and sodium hydroxide (NaOH, 1 M). After Fen-
ton’s treatment, coke wastewater was passed to the next continu-
ous stirred tank reactor (CSTR) where magnesium and phosphate
compounds were added at optimum doses as described in results
Section 4.2. The slow releasing fertilizer magnesium ammonium
phosphate (MAP) which is popularly known as struvite resulted
from the reactions of ammonia of wastewater and the added mag-
nesium and phosphate compounds. MAP got largely settled in the
reactor itself as well as in the two downstream settling tanks.
Clean overflow water from the first settling tank was microfiltered
under low pressure (around 2 bars) in the flat sheet cross flow
microfiltration membrane module (with effective filtration surface
of 100 cm2 each module). Microfiltered water was subsequently
passed to a second nanofiltration membrane module of similar
type via a second settling tank (for final precipitation of the resid-
ual fertilizer granules) where almost all the charged as well as non-
charged particles got separated out from the stream following
Donnan-steric mechanisms of nanofiltration [28]. Finally treated
water was collected as permeate of the nanofiltration membrane
module that was operated at around 15–16 bars pressure.
3.5. Analytics
Analysis for cyanide, ammonia and pH was done in Orion 4 Star
pH ISE Bench top Ion Meter of Thermo Electron Corporation (USA).
The electrodes were first calibrated using the previously prepared
standard of respective compounds. The phenol content was deter-
mined by HPLC (Agilent Technologies 1200 series, USA) with
Zorbax SB-Phenyl column (Germany) having mobile phase metha-
nol: water (70:30) at flow rate 1 mL/min, residence time of 3.5 min
and injection volume of 5 ll. Chemical Oxygen Demand (COD) was
measured by COD Vario Tube Test MR (0–1500 mg/l) of COD ana-
lyzer of LoviBond. Total dissolved solids (TDSs), conductivity and
salinity were measured by InoLab Cond 720, with electrode Tetra-
Con 325 (WTW, Germany). Oil and grease were determined follow-
ing the standard procedures described in the standard methods
[29]. During nanofiltration percentage removal of pollutants were
calculated using the initial concentration (Ci) of the pollutants in
the feed sample and the residual concentration (Cf) in the permeate
side respectively using Eq. (12) as given below.
 
Cf
% removal of pollutants ¼ 1   100 ð11Þ
Ci
3.6. SEM-EDS, XRD, FT-IR, TGA analysis for struvite

Table 2 The collected precipitates were washed with pure water repeat-
Features of the nanofiltration membranes (Sepro, USA) used. edly, air dried for 48 h, and then analyzed by X-ray diffraction
Characteristics Membranes (XRD, D/max-RB, Rigaku, Japan) and Fourier transform infra-red
(FT-IR) spectroscopy (Nicolet iS10, Thermo Fischer Scientific,
NF1 NF2 NF3 NF20
USA). For FT-IR study, 40 mg of KBr (MERCK) was mixed well with
Geometry Flat-sheet Flat-sheet Flat-sheet Flat-sheet 2 mg of finely ground sample for the preparation of transparent
Material Polyamide Polyamide Polyamide Polyamide
Thickness (lm) 165 165 165 165
pellets, for the determination of functional groups. Scanning elec-
tron microscopy with energy dispersive X-ray analysis (SEM-EDS,
Solute rejection (%)
MgSO4 99.5 97 98 98
S-3000, Hitachi Japan) study of MAP was done to get its crystalline
NaCl 90.0 50 60 35 structure, size of the crystal and surface composition of precipi-
pH 2–11 2–11 2–11 2–11 tates. SEM photograph was taken with scanning electron micro-
Maxim Temp (°C) 50 50 50 50 scope at the required magnification at room temperature. TGA
Maxim pressure (bar) 83 83 83 83
and DTGA analysis of struvite was done (DTG-60H, Shimadzu,
Pore radius (nm) 0.53 0.57 0.55 0.54
Japan) to get the heating profile at 10 °C/min.
 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44 37

Fig. 1. Schematic diagram of the membrane-integrated hybrid treatment process for coke wastewater.

4. Results and discussion
4.1. Fenton oxidation for the degradation of cyanide and phenol
Phenol and cyanide were simultaneously removed from the
coke wastewater by Fenton’s reagent (FeSO47H2O and H2O2) by
optimizing the different concentration hydrogen peroxide, ferrous
sulfate and pH. As hydrogen peroxide is a strong oxidizing agent
(oxidation potential 1.77) and dissociate into hydroxyl radicals in
solution that oxidize cyanide compounds to cyanate and further
to ammonia and carbonate ions. This leaves little chance for cya-
nide to get converted into HCN.
data, and square root was chosen (being the best fit in this case)
in both cases (phenol and cyanide removal (%)). From fit summary
section in design, the model F-values as obtained for cyanide re-
moval (145.93) and phenol removal (57.86) implied that models
were significant. Value of P (0.0001) in both cases being less than
0.0500 also indicates that the model terms are significant. The final
regression equation made by analysis of variance (ANOVA) shows
the empirical relationship among the target variables (cyanide
and phenol removal) and the three operating conditions or vari-
ables. The equation in terms of coded factors is represented by
Eqs. (13) and (14) and the statistical parameters obtained from
the ANOVA for these two regression models are listed in Table 4.

Sqrt ðcyanide removal %Þ ¼ þ9:94 þ 1:22  H2 O2 þ 1:25

4.1.1. Results of response surface optimization study using design
 iron salt þ 1:33  pH  0:46
expert software
Experiments were planned and conducted following central  H2 O2  iron salt  0:23
composite design (CCD), considering the minimum and maximum  H2 O2  pH þ 0:33
levels for hydrogen peroxide (1.50–5.50 g/L), iron salt (1.00–3.75
g/L) and pH (3.0–10.0) and the experimental results were incorpo-  iron salt  pH
rated in that design (Table 3). These ranges of the variables param-  0:75ðH2 O2 Þ2
eters were fixed based on the data as reported in the literature in
various studies of phenol and cyanide degradation by Fenton’s
 0:67 ðiron saltÞ2
reagent. In determining the interrelationships of those variable,  2:03 ðpHÞ2 ð12Þ
second-order polynomial equation was fitted to the experimental

Table 3
Experimental response under suggested operating conditions.

STD Run H2O2 (g/L) Iron salt (g/L) pH Response 1 cyanide removal (%) Response 2 phenol removal (%)
14 1 3.50 2.38 12.39 36 12
18 2 3.50 2.38 6.50 99 98
1 3 1.50 1.00 3.00 7 59
15 4 3.50 2.38 6.50 99 98
19 5 3.50 2.38 6.50 99 98
3 6 5.50 1.00 3.00 26 95
6 7 1.50 3.75 10.00 63 34
13 8 3.50 2.38 0.61 4 99
16 9 3.50 2.38 6.50 99 98
12 10 6.86 2.38 6.50 99 98
9 11 3.50 0.06 6.50 28 31
5 12 1.00 1.50 10.0 25 9
4 13 5.50 3.75 3.00 51 100
11 14 0.14 2.38 6.50 33 28
20 15 3.50 2.38 6.50 99 98
10 16 3.50 4.69 6.50 99 98
8 17 5.50 3.75 10.0 98 46
17 18 3.50 2.38 6.50 99 98
7 19 5.50 1.00 10.00 88 25
2 20 1.50 3.75 3.00 35 78
38 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44
Table 4
Statistical parameters obtained from the analysis of variance for the regression
models.
Response R2 Adj. R2 CV (%) S.D AP
Cyanide removal 0.9924 0.9856 4.23 0.32 36.11
Phenol removal 0.9812 0.9642 5.79 0.46 23.98
AP: adequate precision; SD: standard deviation; CV: coefficient of variance.
Sqrt ðphenol removal %Þ ¼ þ9:90 þ 0:97  H2 O2 þ 1:02
 iron salt  1:92  pH  0:24
 H2 O2  iron salt þ 0:40
 H2 O2  pH  0:035
 iron salt  pH
 0:78 ðH2 O2 Þ2
 0:83ðiron saltÞ2  1:15 ðpHÞ2 ð13Þ
The quality of the model developed was evaluated based on the
correlation coefficient R2 and standard deviation value. The closer
the R2 value to unity the smaller the standard deviation implying
more accurate response that could be predicted by the model.
The R2 value for cyanide and phenol removal were found to be
99.24% and 98.12% of respectively. The value of adjusted determi-
nation coefficient was within reasonable agreement with the pre-
dicted R2 in both responses (cyanide and phenol) and it implies
that the model was significant. Effects of H2O2, iron salt and pH
were highly significant as the P values <0.0001 in both cases. The
high significance of the model was also established in the plot of
calculated values against the experimental values of cyanide and
phenol removal % (Fig. 2). Clustering of points around the diagonal
line indicated capability of the model to predict the experiments in
both cases. The coefficient of variance (CV) should not be larger
than 10% and is defined as the percent ratio between the standard
error of the estimate and the mean value of the observed responses
and this is a measure of the reproducibility of the model [30]. Thus,
low CV values in both models (cyanide removal 4.23% and phenol
removal 5.79%) indicated a good reproducibility. Adequate preci-
sion is a measure of the range in predicted response relative to
its associated error or, in other words, a signal-to-noise ratio. Its
desired value is 4 or greater [31]. In the present study, adequate
precision values (cyanide removal 36.11 and phenol removal
23.98) were achieved.
Fig. 3 presents the response surface modelling in a three dimen-
sional representation reflecting the effects of hydrogen peroxide,
iron salt and pH on the cyanide and phenol removal after 1 h of
reaction. As a general trend, it was observed that effects of hydro-
gen peroxide and iron salt on removal of cyanide and phenol was
pH-dependent. At low pH, cyanide degradation by hydrogen perox-
ide and iron salt is very difficult due to presence of cyanide mainly
as HCN gas. At high pH, cyanide present as CN ions, so it reacts
easily with H2O2 and iron salt [32]. Low levels of pH favoured
reduction of phenol which could be traced to generation of hydro-
xyl radicals.
During design of experiments, criteria were selected for optimi-
zation of H2O2 and pH (in the already selected range) at minimum
concentration of iron salt for maximum removal of cyanide and
phenol. Some optimized solutions with different criteria were sug-
gested by the software. From those suggested solutions, two
acceptable solutions were taken as follows: (a) at pH 6.50, H2O2
3.51 g/L and iron salt 2.38, while the expected cyanide and phenol
removal was 99% and 98.23%; (b) at pH 6.09, H2O2 5.45 g/L and iron
salt 1.91 g/L, while the expected 99.002% and 100% cyanide and
phenol removal. As the selected optimum criteria for variables
were not amongst the 20 experiments previously designed by
CCD and were rather assumptions, experiments with selected
criteria were performed in shaker flask level. In the first case, ob-
tained cyanide and phenol removal was 99.5% and 98.6% and in
the second case 99.7% and 100%, respectively. In both the cases,
the predicted responses were in close agreement with the actual
experimental values. Solution (b) i.e. at pH 6.09, H2O2 5.45 g/L
and iron salt 1.91 g/L was accepted as the complete removal of cya-
nide and phenol with minimum concentration of iron salt which
reduced the sludge generation during treatment and avoided iron
contamination in final effluent. The optimum values thus obtained
were used in the continuous process to control the doses of the re-
agent. Fig. 4 shows the HPLC result of phenol concentration before
the Fenton’s treatment and after the treatment with optimized
concentration. Thus after chemical pre-treatment most of the
phenolic compounds were found to get degraded, whatever inter-
mediates were produced during chemical pre-treatment were
completely removed by nanofiltration membrane (as in Section
4.3) as indicated in the final analysis.
4.2. Removal of ammonia through chemical precipitation as struvite
by-product
After Fenton’s treatment, ammonia precipitated out as magne-
sium ammonium phosphate (MAP) from Fenton’s treated effluent
in the struvite by-product unit. The effluent from the Fenton’s
treatment unit contained a high concentration of ammonia
2
(2135 mg/L) due to conversion of cyanide to NHþ 4 and CO3 . In
the first step of MAP precipitation, three different combinations
of the chemicals MgCl26H2O, Na2HPO412H2O, MgO, H3PO4, Ca(H2-
PO4)2H2O and MgSO47 H2O at different molar ratios of Mg2+ and
PO3
4 with respect to NH3 concentration were investigated to find
out the best combinations for maximum precipitation of ammonia
as struvite. The experimental results as shown in Fig. 5 indicate
that the combination of MgCl2.6H2O, Na2HPO4.12H2O and ammo-
nia was the best when used in the molar ratio of 1:1:1. Struvite
precipitation follows Eq. (15):
MgCl2  6H2 O þ NHþ4 þ Na2 HPO4  12H2 O
() MgNH4 PO4  6H2 O # þ2NaCl ð14Þ
However, excess dose of either Mg or2+
PO3
4 did not result in
any significant increase in ammonia removal. The combination of
MgCl26H2O and Na2HPO412H2O was the most efficient in the
ammonium removal, but this also led to high salt concentration
in the effluent in comparison to other two combinations of chem-
icals as evident from Eq. (15). The salts produced at this stage were
subsequently removed by nanofiltration membrane (as discussed
in Section 3.4).
pH exhibits significant role in the struvite production which
ultimately leads to ammonia removal. In terms of thermodynamic
equilibrium, hydrogen ion is released into the solution when stru-
vite is formed, resulting in a decrease in pH. At low pH, hydrogen
ion in reaction solution would inhibit struvite formation resulting
in reduced removal of NHþ 4  N. Under high pH values, other lower
precipitates like Mg3(PO4)2 are formed instead of MAP, resulting in
decreased removal of NHþ 4  N [15]. A pH value of 9.0 has to be
maintained during the reaction by adding NaOH and HCl for better
yield of struvite.
The content of struvite in precipitates has been confirmed
through SEM image, SEM-EDS, FT-IR, XRD and TGA analysis as
shown in the Fig. 6a–e. The FT-IR analysis showed that the infrared
spectrum of the precipitate was close to that of the MAP as re-
ported elsewhere [33]. At 3700–2500 cm1 water-stretching broad
band was observed which indicated the presence of crystalline hy-
drate. The water–phosphate hydrogen bonding was attributed to
 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44 39

Fig. 2. Distribution of experimentally determined values versus statistically predicted values of (A) cyanide removal (%) and (B) phenol removal (%).

2350 cm1 band. The 1683 cm1 band was attributed to the water
HOH bending region. The 1436 cm1 band were characteristics
ammonium band. The XRD patterns and elemental profile gener-
ated by SEM-EDS showed that the precipitates were close to that
of the MAP as reported elsewhere [33,34]. The TGA and DTGA anal-
ysis was done for struvite at 10 °C/min in presence of nitrogen gas.
These data indicate that mass loss begins at a temperature around
55 °C and is essentially complete when temperature reached above
250 °C and 51% corresponds to the following decomposition for
the struvite:
MgNH4 PO4  6H2 O ! MgHPO4 þ NH3 " þ 6H2 O " ð15Þ
DTGA curve of the struvite shows single peak which is attained
at temperature 103 °C due to simultaneous loss of both ammonia
and water molecules which indicates that precipitate material is
struvite.
40 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44

Fig. 3. Response surface plot showing the removal (%) of cyanide (A–C) and phenol (D–F) with variable parameters pH, iron salt and hydrogen peroxide.

Struvite formed during chemical precipitation reaction, were
separated by PVDF microfiltration membrane fitted in the
membrane module in the cross-flow mode. The recovery efficiency
of the used membrane module for MAP was more than 99%. The
recovered struvite can be used as a slow releasing fertilizer for
agricultural use. Table 5 represents the major characteristics of
wastewater after chemical treatments (Fenton’s and MAP precipi-
tation) and its effluent acts as influent for membrane separation.
4.3. Nanofiltration for the removal of trace chemical contaminants: the
final polishing step towards recycling
Two stages of chemical treatment for the removal of cyanide,
phenol and ammonia resulted in increased values of TDS, salinity
and conductivity due to introduction new ionic species and salts
in the solution. During Fenton’s treatment OH radicals were pro-
duced which alone might not be sufficient to degrade all types of
 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44
Fig. 4. HPLC–UV graph for the raw coke wastewater and after treatment.
3
Fig. 5. Effect of different Mg2+: NHþ þ
4 : PO4 molar ratios on NH4  N removals and
selection of compounds at pH 9.0.
chlorophenols and their degraded intermediates. This is possibly
the reason of high COD after two stages of chemical treatment.
Nanofiltration played a significant role in removal of these pheno-
lic intermediate compounds (CODs), ionic species and salts in the
final stage of treatment of coke wastewater. Four different polyam-
ide composite nanofiltration membranes (NF1, NF2, NF3 and NF4)
fitted in a largely fouling-free cross flow module were examined
41
during nanofiltration. At pH values greater than 7.0, most of the
polyamide composite nanofiltration membranes possess negative
zeta potential [25]. Due to the charged nature of the NF membrane,
solutes with an opposite charge compared to the membrane (coun-
ter-ions) are attracted, while solutes with a similar charge (co-
ions) are repelled. Apparent pore size of polyamide NF membranes
can also vary with solution pH. At higher pH values, addition of so-
dium hydroxide leads to an increase in osmotic pressure and ionic
strength, thus reducing the membrane permeability and increasing
rejection. Moreover, functional groups such as carboxyl, hydroxyl
groups were present at the surface of the membrane become
deprotonated at high pH. High pH favors an increased thickness
of diffuse double layer of charged functional groups over the sur-
face of membrane thus reduces the apparent pore size and resulted
in greater rejection charged solutes [35].
The flux data as presented in Fig. 7a and b shows that permeate
flux increased with increase of transmembrane pressure from 5 to
16 bars as well as cross-flow rate from 350 to 800 liters per hour
(LPH) for all nanofiltration membranes. On running the cross-flow
filtration system under various transmembrane pressure and
cross-flow rates, it is possible to find out the critical flux, i.e. the
flux below which minimum fouling occurs. NF2 membrane yielded
the highest flux due to its large pore radius (0.57 nm) whereas the
NF1 membrane (0.53 nm) yielded the lowest flux as permitted by
its smallest pore radius. Cross-flow rate also plays a crucial role
in reducing membrane fouling and optimization of minimizing
membrane area requirement. Increase of cross flow rates, flux in-
creases; this is because of greater convective force that minimizes
cake formation and concentration polarization effects. From above
experiments, an optimum operating pressure and cross flow rate of
16 bars and 800 LPH were arrived respectively, under which the
42 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44

Fig. 6. Surface characterization analysis of struvite (MAP precipitate) obtained during the chemical treatment of ammonia. (a) scanning microscopy analysis of struvite; (b)
energy dispersive X-ray analysis of struvite; (c) Fourier transform infrared spectroscopy analysis of struvite; (d) XRD pattern of the struvite crystel; (e) TGA and DTGA curves
for struvite for heating rate 10 °C min1.

present system could be operated under a stable condition. Mod-
ules should be operated at these critical levels of cross flow rates
which permit maximization of flux for a given membrane surface
area.
Fig. 8 exhibits trend in COD rejection with increase of applied
pressure. 97.5% COD could be reduced by NF1 membrane showing
the best performance compared with the other three investigated
membranes. With increase in the pressure, COD rejection increased
for all the membranes. The solution diffusion mechanism that ap-
plies to nanofiltration plays the major role in the COD rejection.
Solution-diffusion mechanism refers to diffusion of solution
through nanofiltration membrane. In solution diffusion mecha-
nism, solute flux and solvent flux are uncoupled and hence in-
crease of solvent flux with increase of transmembrane pressure
does not result in commensurate increase of solute flux. Rather in-
crease of solvent flux obstructs the transport of solute though the
membrane. Increase in transmembrane pressure leads to increase
in solvent flux. That means solutes rejection will increase with
increase in transmembrane pressure. Solute flux in this case
refers to l/m2/h of solutes (COD) that permeates out through the
 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44 43

Table 5
Characteristics of wastewater after chemical treatment.

Parameter (mg/L) Influent Effluent after chemical treatment (mg/L)

Cyanide 124 0.42
Phenol 162 ND*
Ammonia 1940 48
COD 3856 2270
TDS 24120 37800
Conductivity (mS/cm) 19.12 38.56
Salinity 11.7 25.9
Oil and grease 51 3.5
pH 9–9.5 8.5–9.0
*
Not Detected.

Fig. 8. Effect of applied pressure on COD rejection percentage for all the four
membranes. Operating conditions: transmembranes 16 bar, cross flow rate 800 L/H,
pH 9.0 and temperature 35 °C.

Fig. 9. Effect of applied pressure on TDS, salinity and conductivity rejection

percentage for NF1 membrane. Operating conditions: transmembranes 16 bar,
cross flow rate 800 L/H, pH 9.0 and temperature 35 °C.

Table 6
Characteristics of wastewater after final treatment (membrane separation).

Parameter (mg/L) Influent Final effluent limit Permissible

Fig. 7. Effect of (a) transmembrane pressure (b) cross-flow rate on Flux throughF1, (mg/L) (mg/L)
NF2, NF3 and NF20 membrane. Operating conditions: pressure range 5–16 bar and Cyanide 0.42 ND* <0.1
cross flow rate 300–800 L/H. Phenol ND* ND* <0.5
Ammonia 48 22 <30
COD 2270 102 <250
nanofiltration membrane. Solvent flux is defined as liter of aqueous TDS 37800 1360 –
Conductivity (mS/cm) 38.56 0.9254 –
solvent per meter2 of membrane surface per hour. Salinity 25.9 0.8547 –
Fenton oxidation and MAP precipitation resulted in an effluent Oil and grease 3.5 ND* <10
with 37,800 mg/l TDS, 25.9 salinity and 38.56 mS/cm conductivity pH 8.5–9.0 7.5–8.5 –
reflecting an increase of 56.7%, 121.36% and 73.6% of these three *
Not Detected.
parameters as compared to those in initial raw wastewater. High
salinity resulted from formation of NaCl as a by-product during
MAP precipitation by MgCl26H2O and Na2HPO412H2O (Eq. (15)).
Effect of transmembrane pressure on the rejection of TDS, salinity charge. The high TDS, salinity and conductivity was due to the
and conductivity by NF1 membrane was determined with the charged inorganic ions like bicarbonate ions, Cl, SO24 , etc. and
microfiltrate feed. Fig. 9 shows that with increase of transmem- when these solutes were rejected in contact with negatively
brane pressure from 5 to 16 bars, rejection increased from 73.4% charged NF1 membrane following Donnan exclusion mechanism.
to 96.5%, 78.2% to 96.4% and 76.1% to 97.6% for TDS, salinity and The uncoupling of solute and solvent flux (solution diffusion
conductivity, respectively by NF1membrane. The pH of the solu- mechanism) also plays major role in the removal of TDS, salinity
tion was 9.0, and at this pH, NF1 membrane exhibited negative and conductivity. After MAP precipitation, the remaining ammonia
44 R. Kumar, P. Pal / Chemical Engineering Journal 210 (2012) 33–44
(48 mg/l) was effectively rejected by NF1 membrane (22 mg/l after
NF). In case of ammonia, pore size was effective. The used mem-
branes are not regenerated, but are only rinsed with water when
flux falls drastically. Normally when rinsing with water or chemi-
cal cleaning fails to revive the flux, the membrane is discarded. Ta-
ble 6 shows the major features of wastewater after membrane
separation and its comparison with emission limit values for
wastewater and treated effluent discharged to surface water follow
by most of the countries.
5. Conclusion
The study demonstrates that for recycling water, there needs to
be a paradigm shift in treatment regime for industrial wastewater.
Conventional treatment plants could be turned operationally fast,
economically more viable and environmentally more benign by
appropriate integration of membrane-based treatment with con-
ventional chemical treatment. However, chemical treatment units
should be operated under well optimized conditions where rigor-
ous experimentation using response surface methodology could
be of great help. Future studies should explore raising scale up con-
fidence through modelling and simulation with varieties other
membranes that could be more effective in separation while ensur-
ing prolonged service without significant membrane fouling.
Acknowledgment
Authors are thankful to the Department of Science and Technol-
ogy, Government of India for financial support under DST-FIST
program.
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