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Journal of the Taiwan Institute of Chemical Engineers

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Application of polyurethane@salvadora persica composite for detection

and removal of acidic and basic dyes from wastewater
Elhossein A. Moawed∗, Hala A. Kiwaan, Mariam M. Elshazly
Chemistry Department, Faculty of Science, Damietta University, P.O. Box: 34517, Damietta, Egypt

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

Article history: A novel, stable and inexpensive biosorbent@polymer composite was synthesized by coupling of the
Received 21 February 2017 biosorbent (Salvadora persica roots, SPR) with polyhydroxy polyurethane foam (PPF). The SPR@PPF was
Revised 19 July 2017
characterized using different tools. It was clear that the surface of SPR@PPF contained nanocrystals
Accepted 20 July 2017
particle dispersed in the amorphous phase and also contained 2.4 and 1.0 mmol/g of acidic and basic
Available online xxx
sites. Thermogravimetric curve showed two endothermic peaks at 304 and 396°C due to the cupling of
Keywords: SPR@PPF. The morphology (surface area, pore volume and pore radius) of SPR@PPF are 34.6 m2 /g, 0.053
Polyurethane cm3 /g and 15.4 Ǻ, respectively. The SPR@PPF has successfully utilized in removing of brilliant green (BrG;
Salvadora persica basic dye) and brilliant blue (BrB; acidic dye) from both acidic and alkaline wastewater. The SPR@PPF was
Removal proven efficient for the complete removal of BrG and BrB with a sorption capacity of 202.7 and 142.4 mg/g
Dyes at pH values of 5–7 and 1–2, respectively. Sorption rate constant values (k1 ) are 0.09 and 0.23 min−1 and
Brilliant green
half-life (t1/2 ) are 11 and 4.3 min and the removal process is spontaneous (G is −3.75 kJ/mol). The results
Brilliant blue
sustained the suitability of SPR@PPF as efficient sorbent for the dyes removing.
© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction species such as gold(III), iron(III), manganese(II), atrazine, prome-

The dyeing process of wool, nylon, silk fibers and leather, pa-
per printing, cosmetics and food processing industries are mainly
depending on the organic pigments [1,2]. The most visible pollu-
tants in the effluents discharged from dyeing industries are basic
and acidic dyes [3,4]. The presences of these dyes are very danger-
ous for aquatic life through damaging of water character and re-
ducing the photosynthetic activity of aquatic organisms [5,6]. The
produce of aromatic compounds such as benzidine from organic
dyes has carcinogenic effect and skin diseases [7, 8]. It is very im-
portant that dyeing industries should do the removal of dyes from
the wastewater before discharging into the environment [9,10].
The physical, chemical and/or biological procedures were used
to remove dyes from wastewater [11,12]. The biological degradation
using activated sludge cannot completely remove dyes, physical
processes usually generate toxic sludge, and oxidation processes
are still quite costly for practical application [13,14]. Therefore,
the researchers needed to develop new alternative environmental
friendly applications, locally available, and inexpensive process
[15,16]. Adsorption is one of the most common methods for the
removal dyes from wastewaters [17,18].
The polyhydroxy polyurethane foam (PPF) is a good sorbent due
to high efficiency and low cost process for extracting of different
tryn and terbutryn [11,19–20]. The matrix and terminal of PPF con-
tain different types of active group’s e.g. amino, ether, phenolic and
urethane groups. In this paper, we developed of the PPF surface
by covering with biosorbent to improve its polarity and increase
its sorption capacity. The coupling between PPF and carboxylic
biosorbent (Salvadora persica roots, SPR) [16,21] was through an
ester groups. Firstly, the biosorbent was heat treated at 250°C then
oxidized with concentrated HNO3 . Following by, PPF was refluxed
with carboxylic-SPR to produce the SPR@PPF. The Salvadora persica
trees live in high-temperature, warm and tropical regions. They are
abundant in the desert valleys in Saudi Arabia, Upper Egypt, Sinai
desert, Sudan, and in the eastern regions of India, Pakistan and
Iran. Salvadora persica roots are locally available for use as a good
biosorbent. The properties of SPR@PPF surface were performed
using FTIR, UV–Vis and XRD ray, SEM, BET, DSC and DTA. The
accuracy of the extraction/recovery process and the parameters of
equilibrium, kinetic and thermodynamic were estimated. Finally
the stability of SPR@PPF matrix was studied by recycling it many
times with no significant decrease in its sorption capacity.
2. Experimental
2.1. Apparatus

∗
Corresponding author. All spectrophotometric measurements were performed on
E-mail address: eamoawed@yahoo.com (E.A. Moawed). a JASCO (V-630 UV–VIS Spectrophotometer, Japan). Scanning

http://dx.doi.org/10.1016/j.jtice.2017.07.028
1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: E.A. Moawed et al., Application of polyurethane@salvadora persica composite for detection
and removal of acidic and basic dyes from wastewater, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.07.028
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2 E.A. Moawed et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–7

electron microscope analysis was carried out using JEOL model

JSM-6510LV apparatus, manufactured in the USA. IR spectra were
carried out using KBr disc on a JASCO FTIR-410 spectrometer in
the 40 0 0–40 0 cm−1 regions. X-ray pattern of the CSP@PPF was in-
vestigated by Powder X-ray diffraction (XRD) analysis, it is carried
out with a PAN analytical x, PERT PRO using Cu-Kα X-ray radiation
(λ= 1.540 Å). The BET surface area and pore volume were deter-
mined from nitrogen adsorption and desorption isotherm data ob-
tained at 77 K on a constant-volume adsorption apparatus (Quan-
tachrome NovaWin 3200). Before measurement, the samples were
degassed at 150°C overnight. The total surface area was calculated
by the Brunauer–Emmett–Teller (BET) model. Thermogravimetric
analyses of the samples were recorded on an SDT Q600 Simultane-
ous DSC/TGA Analyzer manufactured by TA Instruments, Inc. (USA).

2.2. Reagents and materials

Fig. 1. Infrared spectra for (A) SPR, PPF and SPR@PPF (B) SPR@PPF:BrG and
SPR@PPF:BrB.
Salvadora persica sticks (Dammam City, Saudi Arabia) were heat
treatment at 250°C for 24 h then blended in a food-processing
blender. A 10 g of Salvadora persica was boiled with 75 mL of con-
centrated HNO3 in a round flask (2 h). The product was washed
with deionized water, dried at 100°C and sieved to obtain homoge-
nous particle size (90–250 mm). The SPR@PPF was prepared by re-
fluxing of 5 g of PPF with 5 g of SPR (1:1) in 200 mL of toluene
(6 h). The black product (SPR@PPF) was left to cool down to room
temperature, filtered off then washed with distilled water followed
by acetone and finally air–dried.
Two commercial textile dyes kindly were supplied by DyStar
(Frankfurt, Germany). The stock solutions of brilliant green and
brilliant blue were prepared by dissolving 0.05 g of each dye in
100 mL of distilled water.

2.3. Recommended procedures

A 25 mL of Br.G and Br.B dyes solutions were shacked with 0.1 g
of SPR@PPF at the desired pH and times. After 60 min, the sample
solutions were filtered then the remained and recovered concen-
trations were estimated spectrophotometrically.
3. Result and discussion
3.1. Characterization of SPR@PPF
The FTIR spectrum of PPF revealed that the broad band of O–
H and N–H groups was observed at 3325–3278 cm−1 and two
bands appeared at 3444 and 1370 cm−1 assigned to O–H (stretch)
and O–H (defuse) aromatic groups. The characteristic absorptions
peaks of the SPR are observed at 3382 cm−1 (O–H of carboxylic
group), 1673 cm−1 (C=O), 1606 cm−1 (C=C) and 1143 cm−1 (C–C)
(Fig. 1A). The O–H and N–H broad band (3325–3278 cm−1 ) of PPF
was shifted to 3677–3106 cm−1 (about 225 cm−1 ) and also the
band at 3382.5 cm−1 of SPR spectrum is disappeared (Fig. 1A). This
variation is due to coupling between SPR and PPF and formation
SPR@PPF through ester group. In addition a new stretching vibra-
tion band was developed at 1506 cm−1 (carboxylate group), indi-
cating that formation of SPR-COO-PPF bond from the reaction be-
tween SPR-COOH and PPF (PUF-OH).
The υ (OH, NH) of the SPR@PPF at 3677–3106 cm−1 are shifted to
3450–3118 cm−1 and 3671–2989 after the sorption of Br.G and Br.B
(Fig. 1B). This may point to the role of the phenolic –OH group of
the SPR@PPF on the sorption process. In addition the new bands
were developed at 1596 cm−1 (C=C aromatic group), indicating the
reaction of SPR@PPF with these dyes forming SPR@PPF: Dye.
The electronic spectra of SPR, PPF and SPR@PPF were recorded
using Nujol mulls method. Fig. 2A shows the absorption spectra of
SPR, PPF and SPR@PPF. The SPR has absorption bands at 201–203,
Fig. 2. Ultraviolet spectra for (A) SPR, PPF and SPR@PPF; (B) SPR@PPF:BrG and
SPR@PPF:BrB.
207–209 and 211 nm assigned to the π –π ∗ transitions. The spec-
trum of PPF contains broadband from 200 to 230 due to the inter-
bonding of OH groups. The higher energy bands in the SPR@PPF
spectrum at 202–205 and 207–211 nm appeared as broad bands
are due to π –π ∗ transitions that are localized on the conjugated
system. While the lower energy bands between 300 and 400 nm
for SPR@PPF are due to π –π ∗ and n–π ∗ transition and are smaller
intensity than in the SPR due to the coupling between PPF and SPR
(Fig. 2A).
The higher energy bands of SPR@PPF are red shifted to 214–238
and 271–288 nm & 206, 209 and 212–204 nm after the sorption of
Br.G and Br.B (Fig. 2B). Also, lower energy bands at 290–380 nm are
shifted to higher wavelengths. The results showed that the shifted
of spectral bands of SPR@PPF are due to the reaction with the dyes.
Acidic and basic sites of the surface of the SPR, PPF and
SPR@PPF were determined using 0.05 mol/L NaOH/HCl solutions.
The acidic sites of SPR, PPF and SPR@PPF are found to be 2.4,
0.4 and 1.0 mmol/g. This result shows that some of the carboxylic
groups (acidic sites) of SPR are consumed after coupling between
SPR and PPF through esterification process. On the other hand, the
basic sites of SPR@PPF (0.8 mmol/g) are greater than that of the
SPR (0.6 mmol/g) and PPF (0.4 mmol/g). By comparing the acidic
sites with the basic ones of the SPR@PPF, it is clear that the total
acidic sites are greater than those of the basic ones (1.0 mmol/g:
0.8 mmol/g = 1.25:1). This result supports the ability of SPR@PPF
to remove acidic or basic dyes according to the attraction between
SPR@PPF and the functional groups of dyes.
The values of electrical conductivity (σ ) of PPF and SPR@PPF
are 6.6 × 10−7 and 2.0 × 10−5 /Ωm. This result indicates that the po-

Please cite this article as: E.A. Moawed et al., Application of polyurethane@salvadora persica composite for detection
and removal of acidic and basic dyes from wastewater, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.07.028
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Fig. 3. (A) pHZPC of SPR@PPF; (B) Effect of pH on the removal of dyes; (C) Zeta
Fig. 4. XDR of (A) PPF and (B) SPR@PPF particle.
potential of SPR@PPF at pH 7.

larity of SPR@PPF is greater than that of the PPF, which is due to

addition of SPR groups.
The surface-charge at different pH values and pH of zero charge
point (pHZCP ) of SPR@PPF were estimated. The value of pHZCP for
SPR@PPF was 4.1–6.3 (Fig. 3A); the surface of the SPR@PPF would
be positively charged at pH values lower than 4.1 due to the pro-
tonation of the surface functional groups in acidic medium. Then
the SPR@PPF surface becomes negative charge over a pH value of
6.3.
The maximum values of ࢞pH for SPR@PPF are +0.8 and −2.5
at pH 2 and pH 11 while those reported for PPF are +0.1 and
−0.6. The obtained results show that the net charge of SPR@PPF
is greater than that of PPF, indicating the high polarity of SPR@PPF
compared with PPF.
Fig. 5. Surface morphology of (A) PPF; (B) SPR@PPF by SEM.
Fig. 3B shows that the maximum removal percentages of Br.G
and Br.B dyes are achieved at pH ranges 5–7 and 1–2, respectively.
Accordingly, the electrostatic attraction between anionic dyes (Br.B)
and the positively charged functional groups on the surface of
SPR@PPF would take place at pH < 2 leading to the complete re-
moval of this dye from the acidic solution at pH 1–2. On the con-
trary, an increase in the medium pH value hinders the Br.B re-
moval due to the increase in the negative charge on the SPR@PPF
surface, which results in electrostatic repulsion between Br.B and
SPR@PPF. While the removal behavior of Br.G onto SPR@PPF is re-
versed when compared to that of the Br.B since Br.G is a cationic
species. At pH 4–12 the net surface charges of the SPR@PPF is neu-
tral and negative that would result in ion exchange or electrostatic
attraction between the surface and the Br.G (cationic dye) leading
to the complete removal of this dye.
The zeta potential is an electrostatic potential at the boundary
dividing the compact layer and the diffuse layer. Over a pH value
Fig. 6. (A) TGA and (B) DSC curves for PUF, PPF and SPR@PPF.
of 6.3, the surfaces of the SPR@PPF would carry a negative charge
and this confirmed by zeta potential which gives a negative value
(−30.7) at pH = 7 (Fig. 3C).
The characteristic diffraction line of PPF and SPR@PPF are ob- PPF matrix through the ester groups with a small size and high
served as broad diffraction bands at 2θ , 21.89°, and 20.79° (Fig. 4). density.
It is clear that the PPF kept its amorphous character, usually ob- Thermal properties of SPR@PPF were evaluated using thermo
served for the aromatic isocyanate-based PPF [22]. The SPR@PPF gravimetric analysis (TGA), differential thermal analysis (DTA) and
was higher band intensity than that of the PPF, indicating the for- differential scanning calorimetry (DSC). The TGA curve of SPR@PPF
mation of the composite without a significant change of the amor- (Fig. 6A) shows a smooth stepwise manner containing five steps of
phous phase. thermal degradation at the temperature ranges of: 24–227, 228–
The surface morphology of PPF and SPR@PPF was investigated 302, 303–351, 352–412, and 413–995°C with a weight loss of 3.3,
using scanning electron microscopy (SEM). Fig. 5 shows SEM im- 25.9, 10.2, 34.6, and 21.8%. The TGA curve of PPF showed that
ages of PPF and SPR@PPF at magnifications of 2500 and 30 0 0x. the thermal degradation occurs through four steps at temperature
The image of PPF reveals a relatively smooth surface with develop- of 35–236, 237–285, 286–343 and 344–396°C with a weight loss
ments of different pores Fig. 5A). While the image of SPR@PPF (Fig. of 0.03, 25.9, 11.9 and 61.7. The 26% remained of SPR@PPF at T
5B) showed that the SPR particles are uniformly anchored into the > 400°C while the remained percentage of PPF is 0.5%; it indicates

Please cite this article as: E.A. Moawed et al., Application of polyurethane@salvadora persica composite for detection
and removal of acidic and basic dyes from wastewater, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.07.028
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Fig. 7. BET curves for sorption and desorption of N2 gas onto SPR@PPF.
that the SPR@PPF is more thermal stability than PPF due to chem-
ical bonding between SPR and PPF.
The DSC and DTA curves for SPR@PPF showed two endother-
mic peaks at 304 and 396°C while the corresponding endothermic
peaks were reported to be 275 and 380°C (Fig. 6B). The shifted of
position of endothermic peaks of the SPR@PPF to higher temper-
ature indicate that the SPR is chemically to the PPF surface. The
endothermic peak of the SPR@PPF at 396°C is more than that of
PPF (380°C). This is may be due the thermal decomposition of in-
terbonding between the SPR and PPF.
The SPR@PPF surface area was calculated using
Brunauer/Emmett/Teller (BET) and Barrett/Joyner/Halenda (BJH)
methods. The N2 sorption isotherm curve shown in Fig. 7 does
not resemble any standard isotherms. The isotherm shows that
no uptake at low relative pressures (˂ 0.155) followed by a more
or less linear uptake of N2 at relative pressures of 0.2–0.97. The
hysteresis loop is closing at a relative pressure of 0.15. For the
polymers, open hysteresis loops would be more likely. The data
of BJH desorption summary reveals that the surface area, pore
volume and pore radius of SPR@PPF are 34.6 m2 /g, 0.053 cm2 /g
and 15.4 Ǻ.
The iodine and methylene blue numbers of SPR@PPF were
calculated to be 3.7 and 0.5 mmol/g. The iodine and methylene
blue numbers of SPR@PPF are compared with other biosorbents
[16,21,23–26]; the SPR@PPF exhibits better capacity values in com-
parison to biosorbents.
The stabilities of SPR@PPF in different solvents were tested.
SPR@PPF showed good chemical stability in the presence of 3 M
HCl, 3 M NaOH, methanol, ethanol, acetone, benzene, p-xylene and
triethylamine.
3.2. Thermodynamic studies
Fig. 1S show the effect of solutions temperature (°C) on the
extraction of brilliant green and brilliant blue dyes from aque-
ous solution using SPR@PPF. The removal percentages of Br.G
onto SPR@PPF were little effecting with increasing of tempera-
ture. While the removal percentages of Br.B dye were decreas-
ing (from 93% to 16%) with increasing of temperature from 25°C
to 45°C then little effect from 45–80°C (Fig. 1SA). The thermody-
namic parameters for the extraction process of Br.G and Br.B dyes
onto SPR@PPF were estimated using the following relationship:
lnK = −H/RT + S/R and G = H − TS. The correlation coeffi-
cients (R2 ) of the plots between ln K and 1/T are 0.756 and 0.925
(Fig 1SB) for extraction of Br.G and Br.B dyes, respectively. The en-
thalpy values (H) for the extractions of Br.G and Br.B dyes are
5.1 and −2.0 kJ/mol, respectively, these values reveal to extraction
process for Br.G is endothermic while the process of Br.B extracted
Please cite this article as: E.A. Moawed et al., Application of polyurethane@salvadora persica composite for detection
and removal of acidic and basic dyes from wastewater, Journal of the Taiwan Institute of Chemical Engineers (2017),
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[m5G;August 18, 2017;17:35]
Table 1
Thermodynamic data for the sorption of dyes onto
SPR@PPF.
Dye G (kJ mol) H (kJ/mol) S (kJ mol)
Br.G −3.7 5.1 0.029
Br.B −3.8 −2.0 −0.19
Table 2
Comparing between kinetic models, chi-square value and rate constant.
Dye Pseudo first order Pseudo second order
R2 X2 k1 , 1/min R2 X2 k2 , μmol g min
Br.G 0.97 0.002 0.09 0.94 0.07 8.11
Br.B 0.83 0.04 0.23 0.99 0.001 0.45
is exothermic. The values of Gibbs free energy (G) are −3.7 and
−3.8 kJ/mol; these values attributed to the extraction process are
spontaneous (Table 1). Finally the entropy (S) of removal of Br.G
and Br.B dyes using SPR@PPF are 0.029 and −0.19 kJ/K mol, respec-
tively. The negative sign of S for extraction of Br.B (acid dye) in-
dicate that the extraction process have a decreased randomness at
the solid/solution interface [27,28]. The results obtained show that
the opposite extraction behavior of brilliant green (endothermic
process) is while the extraction process for brilliant blue (exother-
mic process) and also the opposite of values sign entropy; these
indicate that two different reaction mechanisms occur for each dye
(acidic or basic dye) with SPR@PPF.
3.3. Kinetic studies
The effect contact times on the removal percentages of BrG and
BrB dyes onto SPR@PPF were investigated; sorption experiments
were carried out by shaking of SPR@PPF with dye solutions at dif-
ferent time (1–60 min). Fig. 2SA showed that the times required
for complete removal of the Br.G and Br.B dyes onto SPR@PPF are
found to be 30 and 5 min, respectively. It can be noticed that the
initial removal rate of these dyes is very fast then the rate slowed
down progressively with time and equilibrium is reached within
a period of 5–30 min. Initially all the active sites on the surface
of SPR@PPF are free and dyes molecules can easily occupy these
binding sites. With the progress of the reaction, the binding sites
become saturated and sorption process becomes slower.
Fig. 2SB and SC show that the kinetic parameters study for the
sorption of Br.G and Br.B dyes onto SPR@PPF by pseudo first order
[log (Qe − Qt ) = logQe − kt /2.303] and pseudo second order models
[t /Qt = (1/k2 Qe2 ) + (t /Qe )] [29,30]. Comparing the correlation co-
efficient (R2 ) values reveals that the R2 values for pseudo first or-
der sorption model (0.97 and 0.83) nearly equals those for pseudo
second order kinetic (0.94 and 0.99). Therefore, chi-square value
(X2 = (Qt − Qe )2 /Qe ) were used for comparison between both
models (Table 2). It was observed that the obtained experimental
data of SPR@PPF well fitted pseudo first order model, the values of
X2 0.002 and 0.04 nearly equals to those obtained for pseudo sec-
ond order model were X2 = 0.07 and 0.001. This suggests that the
pseudo first and second orders adsorption mechanism is predomi-
nant and that the overall rate of the dye sorption process appears
to be controlled by chemisorption process.
The values of the rate constant of the sorption (k1 ) were calcu-
lated from the line slope to be 0.09 and 0.23 min−1 . The half-life
of sorption (t1/2 ), rate constant of desorption (k-1 ) and the overall
rate constant (k‘) at room temperature were calculated. The values
of t1/2 are 11.1 & 4.3 min, k− 1 are 0.002 & 0.018 min−1 and k‘ 0.092
& 0.248 min−1 .
The initial rate constant (h = k2 Qe2 ) of Br.G and Br.B dyes are
0.04 and 0.14 min g/μmol. The k2 value of Br.G and Br.B dyes are
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Table 3
Characteristic data of sorption isotherm curves of dyes onto SPR@PPF.

Sorbent Dye Least square equation Correlation coefficient, R2 Capacity

−3
Slope Intercept × 10 mg/g

PPF Br.G 0.14 0.93 0.799 3.2

SPR@PPF Br.G 0.50 0.00 1.0 0 0 202.7
PPF Br.B 0.15 0.82 0.898 4.3
SPR@PPF Br.B 0.28 0.40 0.997 142.4

8.11 and 0.45 μmol g/min. The activation energy for the sorption of Table 4
Br.G and Br.B dyes onto SPR@PPF was estimated (E = −RTlnk2 ). Comparison of maximum sorption capacities of various sorbents for dye re-
moval.
The E value in the range of 1–8 kJ/mol indicates physical adsorp-
tion; a value between 8 and 16 kJ/mol indicates adsorption process Sorbent Dye Q (mg/g) Reference
controlled by ion-exchange mechanism, while a value in the range Iron-Modified Bentonite Brilliant blue 14.2 [34]
of 20–40 kJ/mol is indicative of chemical adsorption. The E val- Sol–gel/CoFe2 O4 composite Brilliant blue 24.2 [35]
ues are −5.17 and 1.98 kJ/mol, these values in indicates that the Banana pith Brilliant blue 4.4 [36]
Cationic starch/ clay composite Brilliant blue 122.0 [37]
removal process for Br.G and Br.B dyes onto SPR@PPF is physical
Carbon slurry Brilliant blue 24.2 [38]
adsorption. Activated carbon Brilliant green 125.0 [39]
Plots of Q versus t0.5 for diffusion of Br.G and Br.B dyes onto Iodopolyurethane powder Brilliant green 154.4 [40]
√
SPR@PPF according to Weber–Morris model (Qt = k1 t) [31] give White rice husk ash Brilliant green 85.6 [41]
2 Amine modified tannin gel Brilliant green 20.4 [42]
straight lines (R = 0.99 and 0.59), which does not pass through the
Peganum harmala-L Seeds Brilliant green 35.9 [43]
origin (Fig. 2SD). The values of diffusion rate constant (ki ) of the PUF@IT@MNPs Brilliant green 224.8 [44]
dyes sorption are 0.08 and 0.03 mmol/g min0.5 . The ki value of Br.G SPR@PPF Brilliant blue 142.4 This work
is greater than Br.B, which reflects that the diffusion rate depends Brilliant green 202.7
on the size of the dye.
The relation between Bt against t for the sorption of Br.G and Table 5
Br.B dyes according to Reichenberg models (Bt = −0.4977 − ln(1 − F) Freundlich and Dubinin Radushkevich isotherm parameters.
& F = (6/R)(Di t/π )1/2 ) [32] was investigated (R2 = 0.98 and 0.83). Dye Freundlich Dubinin Radushkevich
This indicates that partial film along with intraparticle diffusion is
1/n N R2 β E R2
also involved (Fig. 2SE).
The double logarithmic plots of Bangham equation Br.G 0.82 1.22 0.911 −0.0043 10.8 0.894
(log logCo /(Co − Qt m) = log ko m/2.303 + α log t) [33] with the time Br.B 0.73 1.37 0.877 −0.0223 4.7 0.888

yield perfect linear curves, the correlation values coefficient for

the sorption of Br.G and Br.B dyes are 0.99 and 0.68, respectively
(Fig. 2SF). This result shows that the diffusion of these dyes onto
the pores of SPR@PPF is involved in the rate-controlling step. The
values of α are 0.55 and 0.42, showing that the value of α is
depends on the dye size. The regression correlation coefficient
(R2 ) are 0.79, 0.84 and 0.91 for Morris–Weber, Bangham and Re-
ichenberg models for sorption of BrG and Br.B dyes onto SPR@PPF,
suggesting that these models closely fitted the experimental data.
3.4. Equilibrium studies
The effect of the initial Br.G and Br.B dyes concentrations (0.05–
0.6 mmol/L) on the batch capacity (Q) of PPF and SPR@PPF. The
average values of R2 of dye sorption isotherm curves are 0.849
and 0.999 and intercept values are 0.0 0 09 and 0.0 0 02 for PPF and
SPR@PPF (Table 3). It is obvious that the increase of dyes concen-
trations is followed by a subsequent increase in the sorption capac-
ity of SPR@PPF then reached a plateau (maximum capacity) were
obtained. The experimental batch capacities (Q) of the SPR@PPF
for Br.G and Br.B dyes were estimated to be 202.7 and 142.4 mg/g
(Table 3). While the sorption capacities of PPF for Br.G and Br.B
are 3.2 and 4.3 mg/g. It is evident from the achieved results the
SPR@PPF exhibits greater efficiency toward Br.G and Br,B than PPF.
Comparison of the SPR@PPF capacities with that of other sorbents
(Table 4) shows that it has better capacity [34–44].
The equilibrium data estimated from the sorption isotherms
are also basic requirements to understand the mechanism of the
sorption. These data were analyzed using Freundlich (log Qc =
logKF + 1n log Ce ), Langmuir [Ce /Qc = (1/KL b) + (Ce /KL )], Dubinin–
Radushkevich (lnQc = lnKD − R − βε 2 ) models [45–47].
The correlation coefficients of plot of log Qc vs. log Ce (Fre-
undlich model) are 0.911 and 0.877 (Fig. 3SA) while the values
of R2 are 0.804 and 0.615 for the plot of Ce /Qc vs. Ce (Langmuir
model, Fig. 3SB). These values show that the Freundlich model is
more suitable for interpreting the adsorption process (multilayer
sorption on the heterogeneous surface of SPR@PPF (Table 5). The
Freundlich constants (1/n) are 0.82 and 0.73 for sorbed Br.G and
Br.B. The values of 1/n are < 1, which may be attributed to the het-
erogeneous surface structure of the SPR@PPF with a non-uniform
distribution of heat sorption over the surface. The values of n are
1.22 and 1.37, indicating that the sorption of tested dyes is favor-
able [44].
The R2 values for plot between ln Qc and ε 2 (Dubinin–
Radushkevich model) are 0.894 and 0.888 (Fig. 3SC). These values
indicate that accurate assuming that the Dubinin–Radushkevich
model is based on the no homogeneous surface for adsorption pro-
cess. The values of β for the sorption of Br.G and Br.B dyes onto
SPR@PPF are −0.0043 and −0.0223 kJ2 /mol and the values of sorp-
tion energy evaluated are 10.8 and 4.7 kJ/mol.
3.6. Accuracy and precision detection process
The precision and accuracy for the removing of brilliant green
and brilliant blue from wastewater by using SPR@PPF were esti-
mated. The lower of detection limit (LOD = 3 σ ) values for the re-
moval of Br.G and Br.B from six samples of wastewater are 4.6 μg/L
and 4.7 μg/L. The limit of quantitation (LOQ = 10 σ ) are 15.5 μg/L
and 15.8 μg/L. The average recoveries percentages of Br.G and Br.B
by using batch technique are 88.3% and 82.4% with low relative
standard deviation values 1.76% and 1.92% for the analysis of six
samples replicates. The low relative standard deviation values (av-
erage value 1.8%, n = 6), which indicate both good precision and
accuracy of the proposed method. The values of LOD and RSD due

Please cite this article as: E.A. Moawed et al., Application of polyurethane@salvadora persica composite for detection
and removal of acidic and basic dyes from wastewater, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.07.028
JID: JTICE
ARTICLE IN PRESS
6 E.A. Moawed et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–7
to the application of SPR@PPF method for the detection of these
dyes indicate that the SPR@PPF method is efficient for detection of
basic and acidic dyes.
3.7. Sample flow rates
The effect of sample flow rates on the removal percentages of
Br.G and Br.B dyes were estimated using SPR@PPF column (1.0 g;
L = 8 cm). A 25 mL of dye solutions were passed through the col-
umn with a flow rate of 0.4–1.0 mL/min. The effluate solutions col-
lected and recovered dyes were analyzed spectrophotometrically.
The maximum removal percentage (100%) was observed in the
range of 0.4–0.8 mL/min. Flow rates > 1 mL/min led to a subse-
quent decrease in the removal percentage (90%).
3.8. Effect of eluting agents and reusability of SPR@PPF
Eluting agents such as HCl, NaOH, CH3 OH and C2 H5 OH were
examined for the recovery of the studied dyes from SPR@PPF col-
umn. The elution of the Br.G and Br.B dyes was carried out using
the appropriate eluent for each dye. Dyes were completely eluted
using methanol. The SPR@PPF columns were reused about twenty
times after regeneration using methanol without a significant de-
crease in the dye removal percentages and sorption capacities of
SPR@PPF.
3.9. Applications
The validity and accuracy of the SPR@PPF, whether using batch
or column procedures were successfully assessed by the removal of
Br.G and Br.B dyes from wastewater of Damietta industrial city. The
wastewater samples were collected from five places for duration of
seven weeks.
Wastewater samples (n = 6) were collected from a well in New
Damietta city (Br.G and Br.B dyes were not detected). The water
properties of wastewater are turbidity: 4.9, pH: 7,4, conductivity:
982 μS, TDS: 589 mg/L, total alkalinity: 180 mg/L, total hardness:
210 mg/L, Ca: 100 mg/L, Cl: 80 mg/L, SO4 : 65 mg/L, Fe 0.2 mg/L and
Mn 0.1 mg/L. A 25 mL of water samples were individually spiked
with 1 mg of each of the investigated dye, adjusted to the optimum
pH then shacked for 30 min with 0.1 g of SPR@PPF. The remaining
concentration of dyes in the supernatant solution was determined
by the recommended method and the recovery percentages were
found to be ∼90% (RSD = 1.8%). These results show that the inves-
tigated dyes can be removed and also recovered effectively water
using SPR@PPF. The obtained data conferred susceptible accuracy
of the developed method based on the satisfactory values of RSD
and the SPR@PPF is a suitable sorbent proven to be useful in re-
moving both acidic and basic dyes from wastewater.
The brilliant green and brilliant blue dyes were removed from
Nile and drain wastewater in Alzarqa, Kafer Saad and Old Damietta
Cities (turbidity: 4.8, pH: 8.2, conductivity: 380 μS, TDS: 251 mg/L,
total alkalinity: 139 mg/L, total hardness: 120 mg/L, Ca: 70 mg/L, Cl:
30 mg/L and SO4 : 32 mg/L) using the column technique. A 100 mL
aliquot of a wastewater sample was spiked with 1 mg of the tested
dye. The water samples were passed through the SPR@PPF column
at a flow rate of 5 mL/min. Average percentages of the removed dye
from the water samples are 95.2% and 81.1% with RSD 2.24% and
3.85%. The values indicated that SPR@PPF is a suitable sorbent for
the removal of acidic and basic dyes from water samples.
4. Conclusion
Polyurethane foam functionalized with biosorbent was syn-
thesized from coupling between carboxylic biosorbent (Salvadora
persica, SPR) and polyhydroxy polyurethane foam (PPF). The
Please cite this article as: E.A. Moawed et al., Application of polyurethane@salvadora persica composite for detection
and removal of acidic and basic dyes from wastewater, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.07.028
[m5G;August 18, 2017;17:35]
covalently attached between PPF and SPR (ester group) and the
surface properties of SPR@PPF were characterized using SEM, XDR,
TGA and FTIR analysis. The new sorbent was applied for wastewa-
ter treatment by removing of basic dye (brilliant green) and acidic
dye (brilliant blue). SPR@PPF was proven efficient for the com-
plete removal of brilliant green and brilliant blue from waste water
with a sorption capacity of 202.7 and 142.4 mg/g, respectively. The
rate of removal is very fast with sorption rate constant (k1 ) are
0.09 and 0.23 min−1 and half-life (t1/2 ) are 11 and 4.3 min; these
data is useful for environmental technologies in the dyes removal
from wastewater. The removal of brilliant green and brilliant blue
dyes were concluded to be favorable process and their removal was
mainly based on physical mechanism. The thermodynamic param-
eters for removing both dyes were estimated to reveal a sponta-
neous nature (G = −3.75 kJ) of the sorption process.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jtice.2017.07.028.
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