Accepted Manuscript Title: Synthesis, characterization of iodo polyurethane foam and its application for removing of aniline blue and crystal violet from laundry wastewater Author: E.A. Moawed A.B. Abulkibash M.F. El-Shahat PII: DOI: Reference:
S1658-3655(14)00071-5 http://dx.doi.org/doi:10.1016/j.jtusci.2014.07.003 JTUSCI 91
To appear in: Received date: Revised date: Accepted date:
30-12-2013 21-6-2014 5-7-2014
Please cite this article as: E.A. Moawed, A.B. Abulkibash, M.F. El-Shahat, Synthesis, characterization of iodo polyurethane foam and its application for removing of aniline blue and crystal violet from laundry wastewater, Journal of Taibah University for Science (2014), http://dx.doi.org/10.1016/j.jtusci.2014.07.003 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Synthesis, characterization of iodo polyurethane foam and its application for removing of aniline blue and crystal violet from laundry wastewater
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Chemistry Department, Faculty of Science, Damietta University, New Damietta, Egypt Chemistry Department, King Fahd University of Petroleum and Mineral, Dhahran, KSA 3 Chemistry Department, Faculty of Science, Ain Shams University, Egypt
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E. A. Moawed1 A.B. Abulkibash2 and M. F. El-Shahat3
*Corresponding author: E-mail address:
[email protected];Tel: +966505241921; Fax: +96638269936; P.O. Box 2375: Dammam: 31451
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Abstract A new type of sorbent was prepared by treatment of polyurethane foam with HCl followed by replacing the amino functional groups by iodine atoms. The properties
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of iodo polyurethane (iodo-PF) were studied using infrared and ultraviolet/visible spectroscopy, bulk density, pHZPC, elemental and thermal analysis. The removal of
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aniline blue and crystal violet dyes by iodo-PF were investigated using batch technique.
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The results showed that the maximum removal percentage of aniline blue and crystal violet by iodo-PF was in pH range 7- 12. The effect of initial dye concentration on the
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equilibrium adsorption of aniline blue and crystal violet from aqueous solution using iodo-PF was investigated; the plot reveals good correlation with R2=0.995 and the
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intercept value is 0.039. The equilibrium adsorption data were analyzed using Langmuir and Freundlich isotherm models. The capacity of iodo-PF of aniline blue and crystal
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violet are found to be 0.24 and 0.45 mmol g-1, respectively (188.9 and 183.6 mg g-1). The values of G and H were -7.7 kJ mol-1 and -26.1 kJ mol-1, respectively, which indicates
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that the sorption process is spontaneous and exothermic. The sorption rate of the dyes onto iodo-PF is very rapid, 50% removals of dyes occur in 50 sec. The pseudo second order equation is the best model to describe the kinetics of aniline blue and crystal violet sorbed (R2 =0.994). Modified equation ( y ax ) was examined to treat the deviation of 0.n
Morris-Weber model for sorption diffusion mechanism of crystal violet onto iodo-PF. Application of iodo-PF for removing of aniline blue and crystal violet contamination from laundry wastewater was successfully achieved. Keywords: Aniline blue; Crystal violet; Iodo polyurethane; Removal; Wastewater
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1. Introduction Laundry processes include washing (usually with water containing detergents or other chemicals), agitation, rinsing, drying and pressing (ironing). The washing
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process was often be done at range above the room temperature to increase the activities of any chemicals used, increase the solubility of stains, and to kill micro-organisms that
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may be present on the fabric. Various chemicals may be used to increase the solvent
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power of water, such as the compounds in soap root or the ash lye.
Textile laundry wastewater is among the major sources that release hazardous
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dyes into the environment [1]. Dyes are carcinogenic and hazardous for aquatic living organisms [2]. The dyes in water cause human health disorders such as severe damage to
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the kidneys and central nervous system [3]. Aniline blue and crystal violet dyes are
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extensively used in textile industry [4]. These dyes are toxic to mammalian cells, mitotic
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poison and proven potent carcinogen [5]. The removal of dyes from wastewater before their discharge in the environmental is very important due to its polluting effect on the
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underground water.
Many methods are used to treat the wastewater before discharge into the
natural water. Adsorption [6], oxidation [7], microfiltration [8], coagulation [9] and degradation [10] are methods used for the removal of dyes from wastewater. The adsorption methods are the best effective technique which have been successfully applied because of the easy operation, inexpensive, ability to treat concentrated forms of dyes, and have the ability to reuse the spent sorbent via regeneration [11]. Several sorbents are applied to remove the polluted dye from wastewater e.g. polyurethane [12-16] organobentonite [17], carbon [18], Zn2Al-NO3 [19] and miswak [20].
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Polyurethane foam (PF) is a good sorbent to remove some organic and inorganic pollutants from wastewater [21, 22]. The high basisty of PF decreases sorption capacity of PF. This problem demands the preparation of low basicity PF with high
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sorption capacity. In previous studies, we developed PF that contains polyhydroxyl functional group which has high sorption capacity [23, 24]. The polyhydroxy
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polyurethane foam was prepared from commercial PF by replacing the primary amine
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with hydroxyl group. In this work, we prepare iodo polyurethane foam (iodo-PF) by treating the matrix of PF with HCl and diazotization of amino functional groups with
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NaNO2 then replacing the azo groups by iodine atom. Iodo-PF is inexpensive, with good stability and high sorption capacity of removing aniline blue and crystal violet dyes from
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wastewater. The development of iodo-PF with the ability to be recycled many times
2.1. Materials
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2. Experimental
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without significantly decrease in power sorption.
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Aniline blue (C37H32N5O9S3, 786.9 g/mol) and crystal violet (C25H30N3Cl,
407.98) were purchased from BDH (Poole England). Stock solutions of dyes (1 mg mL-1) were prepared by dissolving 0.1 g of dye in 100 mL of H2O. A series of 25 mL of dye standard solutions (0.4-8.0 μg mL-1 dye) were used for calibration curve. Iodo-PF was prepared as follows: 5.0 g of commercial polyurethane foam (PF)
was soaked in 0.5 liter of HCl (2 mol L-1) at 24 hours and then washed with distilled H2O. Polyurethane was diazotized with NaNO2 (50 mL of 2 mol L-1) in ice bath. The diazonium salts of polyurethane were washed with ice cold water and coupled with 2 M KI. The orange iodo-PF was washed with H2O and then dried in air.
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2.2. Apparatus All spectrophotometric measurements were performed using Shimadzu Model
pH meter from Microprocessor pH Meter (HANNA Instruments). 2.3. Recommended procedure
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UV-1800 (Shimadzu Corporation, Japan). The pH measurements were carried out using a
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A 0.1 g of iodo-PF was mixed with 25 mL of the tested dye solution (1µg
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mL-1) then shaken for 30 minutes. The aniline blue and crystal violet concentrations remaining in solution was measured at λ = 599 and 592 nm, respectively. The percentage
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of the removed dye and capacity of iodo-PF (Q, mmol g-1) were calculated using % E (C o C ) C o 100 and Q (C o C )V m equations.
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To determine the iodo-PF surface acid sites, 25 mL of 0.05 mol L-1 NaOH
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solution was added to 0.1 g of iodo-PF, the solution was shaking for 24 hours. 10.0 mL of
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the residual solution was titrated with HCl (0.05 mol L-1) in the presence of methyl orange as an indicator. Also, the basic sites were back titrated with a 0.05 mol L-1 NaOH
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and HCl solutions.
To determine the pHZPC of the iodo-PF, a series of flasks containing 25 mL of
the pH solution range 1–13 (solution was adjusted using HCl and NaOH) was added to 0.1 g of iodo-PF. After 24 hours, the final pH (pHf) of the solutions was measured. The difference between the initial and final pH values (ΔpH = pHf - pHi) was plotted against the pHi. The pHZPC was noted as the pH at which the initial pH equals the final pH. 3. Results and discussion 3.1. Characterization of iodo-PF
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The pHZPC of PF and iodo-PF were shown in figure 1. The pHZPC values of PF and iodo-PF are 8.9 and 6.9, respectively. This result shows that the iodo-PF has less basic than PF. Also, the surfaces sites of the iodo-PF are positively charged at pH lower
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than 6.9 and become negatively charge at pH greater than pH 6.9. The negatively charged of iodo-PF surface is due to free unshared electron pairs of iodine and ether oxygen of
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iodo-PF. The result shows that the iodo-PF is suitable to extract the basic species at pH ≥
Fig. 1
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6.9.
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The amounts of acidic and basic surface sites of iodo-PF are 1.1 mmol H+ g-1 and 0.4 mmol OH- g-1, respectively. The results indicate that the surface sites of iodo-PF
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charged species should be favored.
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are mostly acidic. Accordingly, it could be expected that the sorption of positively
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The percentage composition of carbon, hydrogen and nitrogen in iodo-PF are less than that in PF due to partial hydrolysis of PF (Table 1). Nevertheless, the percentage
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of iodine in iodo-PF was greater than in PUF, it was about 6.3 %. This could be due to addition of iodo group.
The infrared spectra of PF and iodo-PF were tested using the thin film
technique. The spectrum of the PF shows several strong band stretches at 3310.8, 3280.6, 2865.7, 2242.8 and 1596.8 cm-1 due to free -NH2 group, aliphatic hydrocarbon (-CH), free isocyanate (-NCO) and urethane (-NHCOO-) groups, respectively (Fig. 2a). The absorption bands at 3310.8 and 3280.6 cm-1 characteristic of –NH2 group had disappeared in the IR spectrum of iodo-PF. Also, the four new absorption bands had appeared at 409, 420, 450 and 454 cm-1 characteristic of the aromatic C-I groups in the spectrum of iodo-
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PF (Figure 2b). The results indicate that replacing the amino functional groups by iodine atoms in the matrix of iodo-PF. Fig. 2
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For UV-Vis spectrophotometric measurements, a thin film of iodo-PF is
at 700, 425.5 and 281 nm were appeared in iodo-PF spectrum.
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placed in the path of light against PF in H2O medium. The result showed that three peaks
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3.2. Optimum condition for removing of aniline blue and crystal violet dyes The effect of pH on removing aniline blue and crystal violet dyes by using iodo-
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PF is presented in Fig. 1. At pH ≤ 2.0 the removal percentage of the aniline blue and crystal violet is low at first and then increases with the increase of pH values. The
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removal percentages of tested dyes at pH 7-13 are 80-100%. This is due to electrostatic
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interaction between dyes and sorbent (pHZPC = 6.9). The removal percentage of aniline
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blue and crystal violet by using PF are 38.4% and 57.5%, respectively. These results indicate that the iodo-PF is more efficient than PF for removing aniline blue and crystal
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violet.
The effect of initial dye concentration on the extraction of aniline blue and
crystal violet with iodo-PF was studied. The amount of dye extracted for one gram of iodo-PF (Q) was plotted against initial dye concentration. The plot reveals good correlation with R2=0.995 and the intercept value is 0.039 (Figure 3). The capacity of iodo-PF increases by increasing dye concentration and then tends to a plateau. The capacity of iodo-PF for aniline blue and crystal violet are 0.24 and 0.45 mmol g-1, respectively. The sorption capacities of iodo-PF for aniline blue and crystal violet were estimated to be 0.24 and 0.45 mmol g-1, respectively (188.9 and 183.6 mg g-1). It is
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evident from the above results that the developed sorbent exhibits greater capacities towards aniline blue than crystal violet, which indicates that the sorption capacities of the dyes depend on the size of dye molecule. The sorption capacity of iodo-PF is compared
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with other sorbents (Table 2) show that the iodo-PF exhibits better capacity values [20, 25-33].
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Fig.3
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Table 2
The Freundlich (1), Langmuir (2) and Dubinin Radushkevich (3) isotherm
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models were applied (Fig. 3) to interpret the sorption mechanism of aniline blue and crystal violet onto iodo-PF:
(1)
logQc logKF 1n logCe
(2)
lnQc ln KDR 2 & RTln[1 (1 Ce )]
(3)
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Ce Qc (1 KLQm ) (Ce KL ) & RL 1 (1 QmCO )
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Where Ce is the dye concentration at equilibrium in solution (mmol L-1), KL is the
Langmuir sorption constant, Qc is the maximum sorption monolayer capacity, RL is the dimensionless equilibrium parameter. KF and n are the Freundlich constants, the value of n constant give an indication of how favorable the sorption process and KF (mg g–1) is the sorption capacity of the sorbent. KD-R (mol g-1) represents the maximum sorption capacity of sorbent, (mol2 J-2) is a constant related to sorption energy, while is the Polanyi sorption potential. The plots of Ce/Qc vs. Ce and log Qc vs. log Ce of the experimental data according to Langmuir and Freundlich models gave a linear relationship. The results demonstrate that the Freundlich equation provides an accurate description of the sorbed
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aniline blue, which is confirmed by the high value of the determination coefficient (Fig. 3, R2=0.946). While the R2 value of Langmuir model for sorption of crystal violet exceeds 0.998 (Figure 4), suggesting that the model closely fitted with the experimental
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data. These results indicate that the sorption processes are dependent on the size of dye molecule.
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Fig. 4
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The values of were estimated from the slope of linear plots of ln Qc vs. 2 are -0.0083 and -0.0018 kJ2 mol-2 for sorbed aniline blue and crystal violet, respectively
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(Figure 5). The value of sorption energy (mean free energy of sorption, ΔE) can be
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calculated from the equation: 1 2 . The value of (E) evaluated are 7.8 and 16.7 kJ mol-1 for sorbed aniline blue and crystal violet, respectively.
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The effect of temperature on the sorption of aniline blue and crystal violet
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dyes onto iodo-PF was studied. It showed that the sorption of dye decreases with
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increasing temperature. The thermodynamic parameters of aniline blue and crystal violet sorbed onto iodo-PF were evaluated by the following equations:
ln Kc H RT S R
(4)
Kc Ca Ce
(5)
G H T S
(6)
Where Kc is the distribution coefficient, Ca is dye concentration on the iodo-PF and Ce is dye concentration in solution (mmol L-1). The linear plots of ln Kc vs. 1/T (Fig. 4) gave the numerical values of enthalpy (H) and entropy (S) from the slope and the intercept. The values of H for the sorption of aniline blue and crystal violet are -46.3 and -38.3 kJ
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mol-1, respectively. The negative value of H is interpreted as the exothermic chemisorptions process. The values of S are – 128.8 and -99.8 J K-1 mol-1, respectively. The negative values of S indicate decrease of randomness at solid-liquid interface
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during the sorption process. The values of free energy (G) are -7.9 and -8.6 kJ mol-1; the
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negative signs were attributed to the spontaneous nature of sorption process. Fig. 5
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The effect of the dye sample volume (10-100 mL) on the removal percentage (% E) of aniline blue and crystal violet was studied. The maximum sorption
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of tested dyes is in batch factor (V/m) ranges from 100 to 250. Then sorption of dye
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decreases (from 100% to 52%) with increasing of the dye volume in batch factor, V/m ≈ 1000. This result shows that the aniline blue and crystal violet can be effectively removed
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in batch factor 250.
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The effect of various eluting agents like HCl, NaOH, CH3OH, C2H5OH and CH3COCH3 on the stripping of aniline blue and crystal violet dyes from iodo-PF was
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studied. It is observed that the tested dyes were completely eluted from iodo-PF with CH3OH. In addition, the dyes were partially eluting with C2H5OH and CH3COCH3. These results may be due to the matrix of iodo-PF that is swelling in the presence of methanol which is good solvent for aniline blue and crystal violet. The iodo-PF had recycled many times after regeneration using CH3OH then H2O without decreasing the capacity of iodo-PF. The rate of sorption of aniline blue and crystal violet onto iodo-PF has been measured using batch experiment at different time intervals (1-30 min). Time required for the sorption of dyes is 8 minutes. The rate of sorption of dye is very fast (67-
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83% in the first one minute) and then becomes progressively slower with the increasing of time (17-33% sorption dye for 7 minutes). Kinetic modeling of the experimental data helps in finding out the potential
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rate-controlling steps involved in the sorption process. Pseudo first order (7) and pseudo second order (8) models were tested to fit the experimental data for the sorption of aniline
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logQe Qt (logQe ) (k1t 2.303)
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blue and crystal violet onto iodo-PF.
(8)
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t Qt (1 k2Qe2 ) (t Qe ) & h k2Qe2 & t1/ 2 1 Ck2
(7)
Upon comparing the correlation coefficient (R2) values, it was found that the R2
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values of pseudo first order model are nearly equals of R2 values of pseudo second order (Figure 6). Therefore, the Chi-square model was applied for comparing between pseudo
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first order and pseudo second order models. The calculated values of X2 are 0.04 and
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0.003 for pseudo first order and pseudo second order models, respectively. Accordingly,
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we suggest that the pseudo second order adsorption mechanism is predominant. Also, the amount of dyes sorbed at equilibrium (Qe) is calculated form pseudo first order and pseudo second order models. The obtained data shows that the estimated Qe values from the pseudo first order are 20.5 and 0.04 mmol g-1 for aniline blue and crystal violet, respectively. While the calculated values of Qe from the pseudo second order model are 0.47 and 0.48 mmol g-1, respectively. The experimental capacities of iodo-PF for aniline blue and crystal violet were estimated to be 0.24 and 0.45 mmol g-1, respectively these results indicate that the pseudo second order adsorption mechanism is predominant. Fig. 6
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In order to study the diffusion mechanism of the sorption of aniline blue and crystal violet onto iodo-PF, the Morris-Weber (11) equation is applied, Where kM is the
(9)
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rate constant of interparticle transport.
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The plots of Qt versus t0.5 were non-linear, do not pass through the origin and deviate with increasing of time. The result shows that the Morris-Weber equation is not applied
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and could not interpret the diffusion mechanism of the sorption for aniline blue and
3.3. Modified particle diffusion model
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crystal violet onto iodo-PF.
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In case of crystal violet sorbed the plots of Qe versus t0.5 do not pass through the origin and nonlinear. In this regard, we studied the factors affecting the
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diffusion rate of the sorption of crystal violet onto iodo-PF. Also, we applied different
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linear models to explain the particle diffusion mechanism for crystal violet onto iodo-PF. The effect of pH, initial concentration of crystal violet, amount of iodo-PF,
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reaction temperature, size of iodo-PF and particle size of crystal violet were investigated. The results show that the sorption percentage of the crystal violet and capacity of iodo-PF were increased with increasing pH, initial dye concentration, amount of iodo-PF, reaction temperature with decreasing the size of crystal violet and iodo-PF. The deviation of the linear plots of Qt vs. t0.5 was increased by increasing the sorption capacity of iodo-PF. The correlation coefficient values (R2) were decreased by increasing the capacity. In addition, the R2 values were decreased with decreasing the equilibrium sorption time. The intercept values were increased by increasing the sorption capacity and decreasing the equilibrium sorption time. The deviation of linear plot and intercept values depend on the
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sorption percentage, the capacity of sorbent and equilibrium sorption time. The deviation is directly proportional to sorption capacity and inversely proportional to equilibrium time. We conclude that the deviation may depend on the sorption capacity per
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equilibrium time. Therefore, we applied different linear models (10a, 10b, 10c, 10d, 10e and 10f) to treat the deviation plot of Morris-Weber equation also to explain the particle
y ax c
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(10a)
y ax0.5 c
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(10b)
y aenx
(10c) (10d)
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(10e) (10f)
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y ax0.n
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y ax2 bx c y a ln x c
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diffusion mechanism for crystal violet onto iodo-PF:
While comparing the correlation coefficient of the tested models, it shows that
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the R2 values of the 10a, 10b and 10c models are less than the R2 values of 10d, 10e and 10f models. The values of constant in the models 10a, 10d and 10e are nearly equal constant and not detected the actual value of the rate diffusion constant. Model 10d is not simple form. Finally the model (10f) is the best model that can be applied for explaining diffusion mechanism and detecting the rate diffusion constant (Table 3). Table 3 In this section, we applied model (10f, y ax ) which is the simple form to 0.n
explain the particle diffusion mechanism for crystal violet onto iodo-PF. The average value of n is 0.272. The n-value mainly depends on the crystal violet concentration ( n-
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value has decreased from 0.45 to 0.024 with the increasing the concentration from 1.5 to 16 μmol L-1). Also, it depends on the amount of iodo-PF and reaction temperature. The slope value depends on the pH, initial concentration of crystal violet, reaction
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temperature, and particle size of dyes, amount and size of iodo-PF. The value of slope was increased with the increasing pH, initial concentration of crystal violet, reaction
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temperatures, amount and size of iodo-PF. While, it decreased with the increasing of
We applied the equation y ax
. The results obtained show a good
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0.25
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particle size of dyes. R2 value depends on the pH and particle sizes of dyes.
correlation coefficient and lower intercept than that obtained from Qt k M t
0.5
model.
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Nevertheless, the results obtained show that same problem is obtained for the rate of diffusion in high capacity.
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4. Application
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Removing of aniline blue and crystal violet from different wastewater
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samples of El-Dammam industrial city and sea water of Arabian Gulf by iodo-PF was examined. A 25 mL aliquot of water sample (pH values10 and 7.5, respectively) was spiked with 200 g of the dyes. Then the solutions were shacked for 15 min, the remaining concentration of dyes in the supernatant solution was determined. The removal percentage of dyes from the water samples was 90-92%. The obtained results are summarized in Table 4. The results show that the iodo-PF is suitable sorbent to be useful in removing the basic dyes from environmental samples. The RSD% values are found to be in the range of 3–4% which is considered relevant (less than 10%) for real samples. The obtained data conferred susceptible accuracy of the developed method based on the satisfactory values of RSD.
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Table 4 5. Conclusion The new sorbent (iodo-PF) was successfully prepared from polyurethane by
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replacing of –NH2 groups by iodine atoms. The iodo-PF has good characteristics such as rapid extraction, low price, and good chemical stability. Also, it can be used many times
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without losing capacity. Pseudo second order equation is the best model to describe the
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kinetics for extraction of aniline blue and crystal violet. Furthermore, the sorption rate of the dye onto iodo-PF is rapid, 50% of removal dye occurs in first 50 sec. The values of
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thermodynamic parameters indicate that the aniline blue and crystal violet extraction process is spontaneous and exothermic. The average capacity of iodo-PF and removal
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percentage of aniline blue and crystal violet is 0.35 mmol g-1 and 100%, respectively. The
mechanism
of
sorption
of
crystal
violet
onto
iodo-PF
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diffusion
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modified Morris-Weber model (18) was examined for the interpretation of the particle
[ y ax & a f (r ` , r `` , pH , T , C , m) & n f (Qe ) ]. The n-value depends on the '
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0.n
maximum sorption capacity, n f (Qe ) , the ideal values of 0.n ≤ 0.25. It can be seen from modified equation that the plot of Qe against t0.25 must give straight line with intercept equal to ≈zero. Successful application was achieved for laundry wastewater samples in Dammam city.
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[17] D. Shen, J. Fan, W. Zhou, B. Gao, Q. Yue, Q. Kang, Adsorption kinetics and isotherm of anionic dyes onto organo-bentonite from single and multisolute systems, J. Hazard. Mater. 172 (2009) 99-107
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[18] D. Xin-hui, C. Srinivasakannan, W. Qu, W. Xin, P. Jin-hui, Z. Li-bo, Regeneration of microwave assisted spent activated carbon: Process optimization, adsorption isotherms and kinetics, Chemical Engineering and Processing, 53 (2012) 53– 62
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[19] T. Xue, Y. Gao, Z. Zhang, A. Umar, X. Yan, X. Zhang, Z. Guo, Q. Wang, Adsorption of acid red from dye wastewater by Zn2Al-NO3 LDHs and the resource of adsorbent sludge as nanofiller for polypropylene, Journal of Alloys and Compounds, 587 (2014) 99-104 [20] E.A. Moawed, Effect of heating processes on Salvadora persica (Miswak) and its application for removal and determination of aniline blue from wastewater, Journal of Taibah University for Science, 7 (2013) 26–34 [21] E.A Moawed, Sorption behaviour, diffusion mechanism of the iron metal ions in the environmental samples onto polyurethane foam. Analytical Chemistry: An Indian J. 10 (2011) 93-100 [22] E.A. Moawed, A.B. Farag, M.F. El-Shahat, Separation and determination of some trivalent metal ions using rhodamine b grafted polyurethane foam. J. Saudi Chem. Soc. 17 (2013) 47–52 [23] E.A. Moawed, N. Burham, M.F. El-Shahat, Separation and determination of iron and manganese in water using polyhydroxyl polyurethane foam, J. Association of Arab Universities for Basic and Applied Sciences, 14 (2013) 60–66
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[24] E.A. Moawed, M.F. El-Shahat, Synthesis, characterization of low density polyhydroxy polyurethane foam and its application for separation and determination of gold in water and ores samples, Analytica Chimica Acta, 788 (2013) 200-207
ip t
[25] M.A.K.M. Hanafiah, W.S.W. Ngah, S.H. Zolkafly, L.C. Teong, Z.A. Abdul-Majid, Acid Blue 25 adsorption on base treated Shorea dasyphylla sawdust: Kinetic, isotherm, thermodynamic and spectroscopic analysis, Journal of Environmental Sciences 2012, 24(2) 261–268
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[26] E.A. Abdullah, A. Abdullah, Z. Zainal, M.Z. Hussein, T.K. Ban, TiO2/Ag modified penta-bismuth hepta-oxide nitrate and its adsorption performance for azo dye removal, Journal of Environmental Sciences 2012, 24(10) 1876–1884
us
[27] V.K. Gupta, I. Ali, V.K. Saini, Adsorption studies on the removal of Vertigo Blue 49 and Orange DNA13 from aqueous solutions using carbon slurry developed from a waste material, Journal of Colloid and Interface Science 315 (2007) 87–93
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[28] V.K. Gupta, B. Gupta, A. Rastogi, S. Agarwal, A. Nayak, A comparative investigation on adsorption performances of mesoporous activated carbon prepared from waste rubber tire and activated carbon for a hazardous azo dye—Acid Blue 113, Journal of Hazardous Materials 186 (2011) 891–901
M
[29] S. Hong, C. Wen, J. He, F. Gan, Y-S. Ho, Adsorption thermodynamics of Methylene Blue onto bentonite, Journal of Hazardous Materials 167 (2009) 630–633
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[30] E.N. El Qada, S.J. Allen, G.M. Walker, Adsorption of basic dyes from aqueous solution onto activated carbons, Chemical Engineering Journal 135 (2008) 174–184
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[31] R. Baccar, P. Blanquez, J. Bouzid, M. Feki, M. Sarrà, Equilibrium, thermodynamic and kinetic studies on adsorption of commercial dye by activated carbon derived from olive-waste cakes, Chemical Engineering Journal 165 (2010) 457–464
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[32] R. Kumar, R. Ahmad, Biosorption of hazardous crystal violet dye from aqueous solution onto treated ginger waste (TGW), Desalination 265 (2011) 112–118 [33] A. Saeed, M. Sharif, M. Iqbal, Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption, Journal of Hazardous Materials 179 (2010) 564–572
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Figure Captions
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Fig. 1: pHZPC of Iodo-PF and effect of initial pH on the sorption of aniline blue and crystal violet onto Iodo-PF Fig. 2: Infrared spectra of polyurethane foam (PF) and iodo polyurethane foam (Iodo-PF)
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Fig. 3: Effect of initial dye concentration on the sorption of aniline blue and crystal violet onto Iodo-PF
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Fig. 4: Freundlich, Langmuir and Dubinin Radushkevich isotherm models for the sorption of aniline blue and crystal violet onto Iodo-PF
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Fig. 5: Effect of temperature on the sorption of aniline blue and crystal violet onto IodoPF
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d
Fig. 6: Pseudo first order and pseudo second order kinetic models for the sorption of aniline blue and crystal violet onto Iodo-PF
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Table 1
PF
pHZPC
8.9 -
Total basisty, mmol g−1
-
an
Total acidity, mmol g−1
Elemental analysis
IR spectra
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Colour
0.4
59.4, 8.4, 6.8 and 6.3
3310.8 and 3280.6
409, 420, 450 and 454
te
max, nm
1.1
d
υ –C-I aromatic, cm–1
6.9
64.5, 9.1, 7.3 and 0.0
M
C, H, N, and I %
UV–Vis spectra
Iodo-PF
us
Property
cr
Comparison between the properties of PF and iodo-PF
Nil
700, 425.5 and 281
White
Orange
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Table 2
Dye
Treated Shorea dasyphylla sawdust
Acid Blue 25
Qmax (mg/g) 24.4
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Methyl Orange
TiO2/Ag modified Bi5O7NO3
Sunset Yellow
Activated carbon
Orange DNA13
4.5
Acid Blue 113
Methylene Blue
d
Bentonite
11.6
an
Activated carbon (rubber tire)
24.3 and 25.0
Vertigo Blue 49
M
Carbon slurry
Reference
cr
Sorbent
ip t
Comparison of maximum sorption capacities of various sorbents for dye removal
0.8 9.7
[25] [26]
[27]
[28]
151
[29]
Methylene Blue
588, 476 and 380
[30]
Activated carbon derived from olive-waste cakes
Lanaset Grey G,
108.7
[31]
Treated ginger waste
Crystal violet
227.0
[32]
Grapefruit peel
Crystal violet
254.2
[33]
Miswak
Aniline blue
291.2
[20]
Aniline blue
188.9
Crystal violet
183.6
Ac ce p
te
Activated carbons (PAC2, F400 and PAC1)
Iodo-PUF
This work
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Table 3: Application of different linear equation on the diffusion mechanism
Conc., mmol/L 0.0015 0.003 0.008 0.016
Equation y=0.002e0.203x y=0.009e0.089x y=0.054e0.020x y=0.135e0.009x
Conc., mmol/L 0.0015 0.003 0.008 0.016
Equation y=-9E-05x2 + 0.001x + 0.001 y=-0.000x2 + 0.003x + 0.005 y=-0.000x2 + 0.003x + 0.050 y=-0.000x2 + 0.003x + 0.131
R2 0.951 0.742 0.743 0.794
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Equation y=0.000x + 0.001 y=0.001x + 0.001 y=0.001x + 0.054 y=0.001x + 0.133
cr
Conc., mmol/L 0.0015 0.003 0.008 0.016
R2 0.979 0.959 0.958 0.933
te
d
M
an
us
R2 0.852 0.628 0.719 0.786
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Conc., mmol/L 0.0015 0.003 0.008 0.016
Conc., mmol/L 0.0015 0.003 0.008 0.016
Equation y=0.001ln(x) + 0.002 y=0.004ln(x) + 0.009 y=0.004ln(x) + 0.054 y=0.003ln(x) + 0.134
Equation y=0.002x0.45 y=0.009x0.378 y=0.054x0.081 y=0.134x0.024
R2 0.979 0.973 0.974 0.972
R2 0.980 0.931 0.968 0.969
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cr
Table 4:
Removal of crystal violet from wastewater and sea water
Wastewater
200
180.4
Sea water
200
184.8
Recovery %
RSD%
90.2
3.04
92.4
4.39
us
Found, μg
an
Add, μg
Ac ce p
te
d
M
Sample
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te
d
M
an
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24
Fig. 1
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d
M
an
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cr
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25
Fig. 2
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te
d
M
an
us
cr
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26
Fig. 3
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te
d
M
an
us
cr
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27
Fig. 4
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te
d
M
an
us
cr
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Fig. 5
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d
M
an
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Fig. 6
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