Thorium removal from weakly acidic solutions using titan yellow-impregnated XAD-7 resin beads: kinetics, equilibrium and thermodynamic studies
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Abstract
To remove Th(IV) ion from acidic solutions (pH 2.5–2.7), an extractant-impregnated resin (EIR) was fabricated by impregnation of Ambelite XAD-7 resin beads with titan yellow as extractant. Various physicochemical factors such as pH, contact time, temperature, sorbent dose and initial concentration of thorium were investigated. The isotherm data was well interpreted by the Langmuir model. Kinetic experiments data showed that the sorption process could be described by Weber–Morris kinetic model. Thermodynamic studies revealed the feasibility, spontaneity and endothermic nature of sorption process. Desorption experiments showed that the EIR could be reused without significant losses of its initial capacity.
Keywords
Extractant-impregnated resin Titan yellow Amberlite XAD-7 Sorption Th(IV) ionList of symbols
- ARE
Average relative error (%)
- B
Tempkin constant related to the heat of sorption
- b
Langmuir constant related to the free energy of sorption (L mg−1)
- bM
Langmuir constant related to the free energy of sorption (L mol−1)
- C
Intial concentration of thorium ion in solution
- Ce
Equilibrium concentration of the metal ion in the bulk solution (mg L−1)
- Cr
Total concentration of the exchangeable ion in resin phase
- Db
Diffusion coefficient in the solution bulk
- Db
Intra-particle diffusion coefficient (m2 s−1)
- E
Mean sorption energy estimated from Dubinin–Radushkevich (J mol−1)
- k1
Pseudo-first order rate constant (min−1)
- k2
Pseudo-second order rate constant (g mg−1 min−1)
- Kd
Distribution coefficient (mL g−1)
- Kf
Freundlich constant indicative of the relative sorption capacity of the EIR (mg1−(1/n) L1/n g−1)
- Kid
Intra-particle diffusion constant (mg g−1 min−1/2)
- KT
Equilibrium binding constant, Tempkin constant (L g−1)
- I
Intercept in the intraparticle diffusion model (mg g−1)
- m
EIR dose, weight of EIR per liter of solution (g L−1)
- N
Number of measurements
- n
Freundlich constant indicative of the heterogeneity factor
- q0
Maximum sorption capacity based on Dubinin–Radushkevich model (mol g−1)
- qe
Amount of metal ion sorbed per unit weight of EIR at equilibrium (mg g−1)
- qe.cal
Theoretical q e values obtained from the kinetic or isotherm models (mg g−1)
- qe.exp
Experimental q e values (mg g−1)
- qmax
Maximum sorption capacity; Langmuir constant (mg g−1)
- qmax,exp
Maximum experimental sorption capacity (mg g−1)
- qt
Amount of metal ion sorbed at any time t (mg g−1)
- R
Universal gas constant (J mol−1 K−1)
- R2
Correlation coefficient
- r0
Mean radius of the EIR particles (m)
- R%
Removal efficiency (%)
- RL
Dimensionless separation factor
- RMSE
Root mean square error (%)
- T
Temperature (K)
- t
Time (min)
- V
Solution volume (L or mL)
- W
Weight of EIR (mg)
- Xt
Degree of fractional attainment to equilibrium at time t
Greek letters
- ΔG°
Gibb’s free energy change (J mol−1)
- ∆H°
Enthalpy change (J mol−1)
- ∆S°
Entropy change (J mol−1 K−1)
- Δq%
Normalized standard deviation (%)
- α
Elovich constant indicative of the initial sorption rate (mg g−1 min−1)
- β
Elovich constant indicative of the desorption constant (g mg−1)
- δ
Dubinin–Radushkevich constant related to the sorption energy (mol2 J−2)
- ε
Polanyi potential
- ω
Thickness of the liquid film surrounding the sorbent beads
Introduction
Radioactive metals, including thorium, endanger environment and all forms of life through radiation release and chemo toxic effects. Unfortunately, in addition to natural sources, spread of radioactive metals in the environment goes along with all stages in some industries and, therefore, radioactive pollution originated from these sources has been rapidly increased in the last decades. This problem has triggered extensive investigations aiming at development of more suitable technologies for removal of radioactive metals from polluted waters and wastewaters. Among the various removal technologies reported in the literature, sorption is one of the suitable methods for water and wastewater treatment. Its advantages include simplicity, flexibility, high efficiency, cost-effectiveness, ease of operation and low consumption of reagents [1, 2, 3, 4, 5, 6, 7, 8, 9, 10].
Macroporous polymers, including XAD series resins, are desirable supports for sorption systems owing to the properties of their matrix such as chemical and mechani-cal stability, uniformly accessible pores and high surface area [11]. In addition to their applications as desirable sorbents for the sorption of organic pollutions, XAD resins have been widely applied as promising supports for synthesizing selective chelating ion exchange sorbents for interested metal ions [12, 13, 14, 15, 16, 17]. To enhance the capability and selectivity of the macroporous polymeric resins, few modification approaches, including impregnation of the polymeric beads with desired extractants [12, 14, 15, 18, 19, 20], have been attempted in the last decades. Since the impregnation process does not require surface activation of polymeric supports, which is very difficult and time consuming, impregnating of special chelating extractants into/onto the macroporous polymeric supports is the most convenient and simplest approach to preparing selective chelating ion exchange resin, and extractant-impregnated resins can be easily prepared by contacting the solution of appropriate extractants with desired polymeric supports [21]. Therefore, in the last decade, many extractant molecules containing functional groups with an affinity for specific metal ions have been used for preparing advantageous EIRs and removing toxic metal ions from aqueous solutions [5, 13, 16, 21, 22, 23, 24, 25, 26, 27, 28, 29].
Experimental
Material and apparatus
All reagents used in this research were analytical grade and purchased from Merck (Dramstate, Germany), except Amberlite XAD-7 resin (surface area 500 m2 g−1, average bead diameter 560 µm, pore diameter 45.0 nm and bead size 20–60 mesh) which was supplied by Rohm & Haas (USA). The stock solution of 500 mg L−1 Th(IV) was prepared by dissolving the appropriate amount of its nitrate salt in 50 mL of 1 M HNO3 solution and diluting to the mark (1 L) with deionized water (Milli-Q Millipore, 18.2 MΩ cm−1 resistivity) and all the working solutions of given concentrations were obtained by diluting this stock solution. NaCl solution (2.0 M) was used for adjusting the ionic strength of working solutions at 0.01 M, and the pH of solutions was adjusted using 1.0 M HCl or 1.0 M NaOH solution. The reagent solution of 1.0 % Arsenazo III was prepared daily by dissolving 0.2500 g of this reagent in 25 mL deionized water.
A PHS-3BW Model pH-meter (Bel, Italy) with a combined glass–calomel electrode was employed for measuring pH values in the aqueous solutions. A Gallenkamp automatic shaker model BKS 305-010, UK, was used for the batch experiments. To compare the FT-IR spectra of synthesized EIR with commercial polymer, the spectra were recorded using AVATAR 370-FTIR Thermo Nicolet instrument within the range of 400–4000 cm−1 wave number, using KBr discs. The morphological change of XAD-7 after the impregnation was observed by a field emission scanning electron microscope (FE-SEM, Hitachi S4160) under an acceleration voltage of 30.0 kV. A Shimadzu model UV-1601PC spectrophotometer was used for all absorbance measurements with one pair of 10 mm quartz cells.
Preparation of the EIR
Prior to conduct the sorption experiments, 0.05-g portions of dry EIR were suspended in 10 mL 3 M HCl for 24 h and, then, the beads were thoroughly rinsed with deionized water [21].
Sorption and desorption experiments
In the above equations, q t (mg g−1) is the amount of Th(IV) sorbed onto the sorbent at time ‘t’, q e, (mg g−1) is the amount of Th(IV) sorbed onto the sorbent beads at equilibrium, q max,exp (mg g−1) is the amount of Th(IV) sorbed onto the sorbent beads after several sorption equilibrium cycles, C 0 (mg L−1) is the initial concentration of Th(IV) in the aqueous phase, C t (mg L−1) is the Th(IV) concentration remaining in the solutions at time ‘t’, C e (mg L−1) is the equilibrium concentration of Th(IV) in the aqueous phase, V (L; mL) is the volume of the solution and W (g) is the weight of the sorbent beads used in the sorption experiments.
For the study of pH dependency of Th(IV) sorption onto the EIR beads, the radionuclide solutions with different initial concentrations of 25, 50 and 75 mg L−1 were shaken at 180 rpm for 60 min at ambient temperature (298 K). The pH value of working solutions was adjusted by 1 M NaOH or 1 M HCl solution.
The effect of agitation speed was studied in the range of 0–300 rpm using 100-mL aliquots of aqueous solution (pH 2.6) containing 50.0 mg L−1 Th(IV) and shaking them for 60 min at ambient temperature (298 K).
To evaluate the effect of EIR dosage on the removal extent, 10.0–100.0 mg of fresh EIR was added to 100 mL of aqueous solution (pH 2.6) containing 100.0 mg L−1 Th(IV) and the mixture was shaken at 180 rpm for 60 min at ambient temperature (298 K).
Equilibrium studies were conducted by contacting the EIR beads with thorium solutions (pH 2.6) with various initial concentrations (0–100 mg L−1) and shaking the mixtures at 180 rpm for 60 min. The equilibrium experiments were performed at different temperatures.
To investigate the kinetic behavior of the sorption process, EIR beads were added to the Th(IV) solutions (pH 2.6) with three different concentrations (25, 50 and 75 mg L−1) and the samples were agitated for constant time periods varying from 1 to 90 min at 180 rpm and 298 K.
The effect of temperature on the sorption of Th(IV) ion was investigated by conducting equilibrium experiments at 288, 298, 308, and 318. In addition, the distribution constant, K d, obtained at the mentioned temperatures was utilized to compute the thermodynamic parameters.
To conduct regeneration studies, the thorium-loaded EIR beads were washed thoroughly with deionized water. Then, desorption of Th(IV) was performed by shaking the thorium-loaded EIR beads with 10 mL of 2 M HCl solution, after equilibrium was reached, the EIR beads were removed from the eluent solution and the concentration of Th(IV) ion was measured to determinate the amount of desorbed radionuclide.
Results and discussion
Effect of pH on Th(IV) sorption by EIR
Effect of agitation speed on the sorption process
Effect of sorbent dose
Effect of contact time and initial concentration
Equilibrium studies and effect of temperature
The equilibrium studies are generally useful for understanding the sorption mechanism and gaining ability to design an industrial sorption system. A solute can be sorbed from aqueous media onto surface of a solid support by several mechanisms. The sorption mechanism is dependent on the nature of sorption sites, surface properties, affinities of the sorbent sites, the type of the sorbate and the bulk properties of the aqueous solution (like pH). For interpretation of the equilibrium sorption data at different temperatures, the Langmuir [35], Freundlich [36], Tempkin–Pyzhev [37] and Dubinin–Radushkevich [38] isotherm models were utilized Eqs. (9)–(12).
The linear form of the Langmuir equation is given by
The E magnitude can give an idea about the type of sorption process whether it is physical or chemical.
Isotherms parameters statistical indices for the sorption of Th(IV) ion onto TY/XAD-7 surface at different temperatures
Isotherm model | Temperature (K) | |||
---|---|---|---|---|
288 | 298 | 308 | 318 | |
Langmuir | ||||
R 2 | 0.9998 | 0.9997 | 0.9996 | 0.9999 |
q max (mg g−1) | 145.0 | 147.1 | 149.7 | 152.1 |
b (L mg−1) | 1.725 | 2.073 | 2.441 | 2.928 |
∆q e (%) | 2.499 | 2.672 | 2.817 | 2.895 |
ARE (%) | 0.062 | 0.071 | 0.079 | 0.084 |
RMSE | 1.271 | 1.201 | 1.212 | 1.299 |
Freundlich | ||||
R 2 | 0.8117 | 0.8142 | 0.8199 | 0.8205 |
K F (mg1−(1/n) L1/n g−1) | 74.96 | 73.91 | 70.08 | 64.86 |
n | 2.931 | 3.018 | 3.160 | 3.347 |
∆q e (%) | 32.76 | 33.26 | 34.28 | 34.34 |
ARE (%) | 10.73 | 11.04 | 11.75 | 11.80 |
RMSE | 23.22 | 23.24 | 23.62 | 23.77 |
T–P | ||||
R 2 | 0.9635 | 0.9527 | 0.9516 | 0.9509 |
Kt (L g−1) | 25.28 | 38.24 | 48.35 | 62.56 |
B | 24.32 | 24.04 | 23.14 | 21.71 |
∆q e (%) | 26.47 | 23.81 | 15.83 | 15.72 |
ARE (%) | 7.005 | 5.671 | 2.506 | 2.470 |
RMSE | 10.41 | 9.219 | 9.006 | 8.838 |
D–R | ||||
R 2 | 0.8502 | 0.8557 | 0.8621 | 0.8765 |
E (kj mol−1) | 14.73 | 15.81 | 16.65 | 17.05 |
q 0 (mol g−1) | 2.997E−03 | 2.845E−03 | 2.721E−03 | 2.687E−03 |
∆q e (%) | 49.43 | 51.28 | 52.89 | 56.30 |
ARE (%) | 24.44 | 26.29 | 27.97 | 31.70 |
RMSE | 18.50 | 18.40 | 18.85 | 19.19 |
q max,exp (mg g−1) | 144.43 | 146.52 | 149.35 | 151.79 |
The results reported in the Table 1 also show that an increase in the temperature results in a relative increase in both theoretical and experimental sorption capacities, indicating the greater equilibrium constants at the higher temperatures and endothermic natural of sorption process. Also, increasing the temperature caused increase in the Langmuire constant, b, indicating the higher sorption rates at the higher temperatures, which can be attributed to both decrease in the solution viscosity and increase in the Th(IV) ion mobility in the solution.
The Langmuir isotherm model also provided the best fit for the sorption of thorium ion onto perlite [45], n-Benzoyl-n-phenylhydroxylamine impregnated Amberlite XAD-4 [46], nanoporous ZnO [6], electrospun polyvinyl alcohol/titanium oxide nanofiber [47], poly(methacrylic acid)-grafted chitosan/bentonite composite [48], carboxylate-functionalised graft copolymer derived from titanium dioxide-densified cellulose [49], PAMAM dendron-functionalized styrene divinyl benzene [11], Tannin-modified poly(glycidylmethacrylate)-grafted zirconium oxide densified cellulose [50], and Cystoseira indica alga [51].
Kinetic modeling
- (i)
Mass transfer of thorium ions from bulk solution to TY/XAD-16 surface (called solution mass-transfer, or bulk diffusion).
- (ii)
Mass transfer of thorium ions through the liquid film surrounding the EIR beads (called external mass-transfer, or film diffusion).
- (iii)
Mass transfer of thorium ions through the bead pores (called internal mass-transfer, or intra-particle diffusion).
- (iv)
Chemical reaction of thorium ions with available titan yellow molecules on the interior surface of pores.
Therefore, to find out the controlling mechanism of sorption process, such as solution mass-transfer, film diffusion, intra-particle diffusion and chemical reaction, the datasets in Fig. 6 were fitted on several kinetic models and the results are discussed below.
Pseudo-first-order kinetic model
Kinetic parameters and statistical indices for the sorption of Th(IV) ion by the TY/XAD-7 beads at different initial concentrations and 298 K
Kinetic model | C 0 (mg g−1) | ||
---|---|---|---|
25 | 50 | 75 | |
Weber–Morris | |||
k ip (mg g−1 min−1/2) | 4.147 | 7.992 | 11.482 |
I | 0.386 | 0.430 | 0.448 |
R 2 | 0.994 | 0.995 | 0.996 |
∆q (%) | 2.264 | 2.334 | 2.985 |
ARE (%) | 0.051 | 0.055 | 0.089 |
RMSE | 0.723 | 1.263 | 1.811 |
Elovich | |||
α (mg g−1 min−1) | 12.49 | 25.07 | 34.64 |
β (g mg) | 0.091 | 0.046 | 0.033 |
R 2 | 0.929 | 0.896 | 0.893 |
∆q (%) | 28.59 | 29.80 | 29.61 |
ARE (%) | 8.173 | 8.880 | 8.766 |
RMSE | 3.396 | 8.317 | 11.567 |
Pseudo-first-order | |||
k 1 (min−1) | 0.063 | 0.072 | 0.075 |
q e,cal (mg g−1) | 53.4 | 123.0 | 175.5 |
R 2 | 0.965 | 0.9159 | 0.880 |
∆q t (%) | 34.00 | 65.76 | 70.61 |
ARE (%) | 12.25 | 43.25 | 49.86 |
RMSE | 3.887 | 12.39 | 18.85 |
Pseudo-second order | |||
k 2 (g mg−1 min−1) | 1.825E−3 | 8.450E−4 | 6.092E−4 |
q e,cal (mg g−1) | 54.35 | 109.89 | 151.5 |
R 2 | 0.939 | 0.916 | 0.914 |
∆q (%) | 37.07 | 37.51 | 37.57 |
ARE (%) | 13.74 | 14.07 | 14.11 |
RMSE | 4.270 | 9.351 | 13.19 |
q e,exp (mg g−1) | 49.35 | 98.04 | 136.36 |
Pseudo-second order model
Elovich kinetic model
Intra-particle kinetic model
The corresponding kinetic parameters for the Weber–Morris model were determined from the plots presented in Fig. 9, and the results are listed in Table 2. The results showed that k ip increased with increasing initial Th4+ concentration and the correlation coefficients were in the range of 0.994–0.996 (Table 2). The higher correlation coefficients (R 2), lower statistical indices and large difference between q e,cal and q e,exp for Weber–Morris model indicate that the sorption process is controlled by pore diffusion which is the rate-controlling step in the sorption of thorium onto TY/XAD-7 beads. This model also indicates that the intra-particle diffusivity is constant and the direction of the diffusion is radial [59, 60]. The applicability of the Weber–Morris model to describe the kinetic characteristics of the sorption of some other radionuclides using chelating ion-exchange polymers have been also reported in some previous studies. For example, similar phenomena have been observed for thorium sorption onto many sorbents, such as polyhydroxyethylmethacrylate-hydroxyapatite [61], 1,4-diaminoantraquinone/1,4-dihydroxyantraquinone impregnated XAD-16 [5], calcined diatomite [62], TBP-impregnated sorbent [63] etc.
The slopes, intercepts and R2 values obtained from correlating data with the functions of HPDM model
Concentration | \(- { \ln }\left( {1 - X_{t} } \right)\) | \(- { \ln }\left( {1 - X_{t}^{2} } \right)\) | ||||
---|---|---|---|---|---|---|
Slope | Intercept | R2 | Slope | Intercept | R2 | |
25 | 0.0441 | 0.1561 | 0.9751 | 0.0282 | −0.0005 | 0.9988 |
50 | 0.0467 | 0.1656 | 0.9760 | 0.0306 | 0.0005 | 0.9987 |
75 | 0.0503 | 0.1747 | 0.9774 | 0.0339 | 0.0009 | 0.9992 |
The values of D ip obtained from HPDM model for the sorption of thorium by the EIR beads at different initial concentrations
Initial concentration (mg L−1) | D ip (m2 s−1) |
---|---|
25 | 6.73 × 10−9 |
50 | 7.30 × 10−9 |
75 | 8.09 × 10−9 |
Evaluation of thermodynamic parameters
Thermodynamic parameters for the sorption of thorium by the EIR beads as a function of temperature
Temprature (K) | Parameters | ||
---|---|---|---|
∆G° (kJ mol−1) | ∆H° (kJ mol−1) | ∆S° (J mol−1 K−1) | |
288 | −30.89 | ||
298 | −32.43 | 13.33 | 153.5 |
308 | −33.93 | ||
318 | −35.51 |
Desorption and reusability
Conclusion
In this research work, titan yellow-impregnated XAD-7 resin (TY/XAD-7) was synthesized and its sorption behavior was investigated for Th(IV) removal from acidic solutions. The sorption of Th(IV) ion onto TY/XAD-7 was investigated for pH, agitation speed, sorbent dose, initial concentration, time, temperature and reusability. The sorbent showed a high affinity to Th(IV) ion, and the maximum sorption of Th(IV) ion occurred at pH range of 2.6–2.7. The sorption process was relatively fast and the equilibrium could be reached within 55 min. The equilibrium data were analyzed using several isotherm models. Both the correlation coefficients and statistical indices indicated that the Langmuir model fits better than the other isotherm models for the sorption of thorium ion onto the TY-XAD-7 beads. The kinetic data fitted with the Weber–Morris model and, under agitation speed and other experimental conditions applied in this work, the resistance to intra-particle diffusion had the greatest impact on the control of sorption process. In addition, the kinetics was correlated with homogenous particle diffusion model (HPDM) for estimating the intra-particle diffusion coefficients, D ip values, which were of the order of 10−9 m2 s−1. Sorption capacity appeared to increase at elevated temperatures and the thermodynamic studies indicated that the nature of sorption process is spontaneous and endothermic. The radionuclide bound to the sorbent surface was efficiently desorbed by 2 M HCl solution and the recycling was shown to be efficient for at least 25 sorption/desorption cycles.
The studies performed in the present study exhibited that TY/XAD-7 resin can be considered as a good sorbent for thorium in terms of high sorption capacity, selectivity, cost, rapid sorption, etc. Also, since the macroporous XAD series resins are completely stable in all aqueous solutions, including acidic ones, TY/XAD-7 can be utilized as an industrial compatible sorbent for the removal of Th(IV) ion from acidic streams and matrices.
Notes
Acknowledgments
We acknowledge the financial support of the present work from the Central Research Council of Sabzevar University of Medical Sciences (Grant 3930101102). In addition, the authors wish to take this opportunity to express their sincere thanks to Prof. Mohammad Mohammad–Zadeh, the research council president of Sabzevar University of medical Science, for his great helps and supports during the experimental works.
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