Journal of Nuclear Science, Engineering and Technology (JONSAT)
In cooperation with the Iranian Nuclear Society

Synthesis of Clinoptilolite-Polyacrylonitrile Nano Composite for removal of zirconium from aqueous solution: Investigation and evaluation of effective parameters on sorption process, kinetic, thermodynamic and adsorption isotherms parameters

Document Type : Research Paper

Authors

S. Habibollahi 1
M. Iravani 2
A.R. Zarean 1

1 Department of Chemistry, Payame Noor University, P.O. Box: 19395-4697, Tehran, Iran

2 Reactor and Nuclear Safety Research School, Nuclear Science and Technology Research Institute, P.O.Box: 81465-1589, Esfahan - Iran

https://doi.org/10.24200/nst.2020.1100
Abstract
In the present research, composite adsorbents consisting of nano clinoptilolite and polyacrylonitrile (PAN) were prepared. The synthesized composites were characterized by XRD, XRF, FT-IR, DTG and SEM analysis techniques, and finally the adsorption behavior of the composites toward zirconium was investigated. In this nano adsorbent, nano-zeolite clinoptilolite acts as an active component for the absorption of zirconium ions, and polyacrylonitrile plays a bining role. In addition, by changing the size of zeolite particles from micrometer to nanoscale, the adsorption capacity and the kinetic of the adsorption process was increased significantly. The absorption rate by nanocomposites was very rapid and more than 75% of the maximum absorption capacity for zirconium was obtained in the first 5 hours. The SEM image showed that zeolite particles are bonded to each other by a PAN polymer. The porous structure of the nanocomposite allowed permeation of the ions from solution into nanocomposite beads and reaching the ion exchange sites. The effect of pH, initial ion concentration, contact time, and temperature were examined. The optimum contact time and pH were 24 h and 2, respectively. The maximum adsorption capacity of the composite was 18.65 mg.g-1 and the composite was able to remove 80% of Zr+4 from 0.01 meq.mL-1 aqueous solutions. The kinetic and thermodynamic parameters were extracted. The experimental data were well fitted with a pseud-second order kinetic model with good correlation coefficients. In addition, the theoretical values obtained from the equation showed a good agreement with experimental values. Therefore, the pseudo-second order kinetic equation can be considered as a suitable model for interpreting experimental data. The agreement of the experimental data with the Pseudo-second order kinetic model showed that overall rate constant controlled by chemical sorption. In addition, the constant rate of absorption by nanocomposites was higher than that of a clinoptilolite-polyacrylonitrile-macrometric composite. In other words, the absorption of zirconium ion on nanocomposite was significantly higher than that of a zeolite composite with macro dimensions. Positive ΔH° and negative ΔG° were indicative of the endothermic and spontaneous nature of process. The equilibrium data were analyzed by the Langmuir, Freundlich, and Dubinin–Radushkviech isotherm models. D-R isotherm model indicated that ions were uptake through an ion exchange process. The obtained RL values range between 0 to 1, indicating Zr adsorption was favorable. Comparison of Q0 values for adsorbents showed that the nanocomposite has the highest absorption capacity for zirconium ion. This high Q0 value can be explained by the nanoscale size of the composite.

Highlights

1.             H. Faghihian, M. Iravani, M. Moayed, Application of PAN‐NaY Composite for CS+ and SR2+ Adsorption: Kinetic and Thermodynamic Studies, Environ. Prog. Sustain. Energy, 34, 999 (2015).

 

2.             M. Ghaemi, M. Torab-Mostaedi, M. Ghannadi-Maragheh, Characterizations of strontium (II) and barium (II) adsorption from aqueous solutions using dolomite powder, J. Hazard. Mater. 190, 916-921 (2011).

 

3.             Y.Q. Zhang, et al. Selective separation behavior of silica gel for zirconium in simulated high level radioactive liquid waste, J. Radioanal. Nucl. Chem, 247(1), 205-208 (2001).

 

4.             Q. Liang, H. Jing, D.C. Gregoire, Determination of trace elements in granites by inductively coupled plasma mass spectrometry, Talanta, 51 (3), 507-513 (2000).

 

5.             T. Onishi, S. Koyama, H. Mimura, Removal of zirconium from spent fuel solution by alginate gel polymer, Progress in Nuclear Energy, 82, 69-73 (2015).

 

6.             L.H.J. Lajunen, P. Peramaki, Spectrochemical Analysis by Atomic Absorption and Emission, Royal Society of Chemistry: Cambridge, (2004).

 

7.             J. Startý, J. Ruzicka, Metal chelate exchange in the organic phase—I: Theory: application in spectrophotometry and complex chemistry, Talanta, 14(8), 909-920 (1967).

 

8.             G.A. Welford, E.L. Chiotis, R.S. Morse, Submicroanalysis by Radiochromatography, Anal. Chem., 36 (12), 2350 (1964).

 

9.             B.A. Thompson, B.M. Strause, M.B. Leboeuf, Gamma Spectrometric and Radiochemical Analysis for Impurities in Ultrapure Silicon, Anal. Chem., 30, 1023-1027, (1958).

 

10.          R.F. Buchanan, J.P. Hughes, C.A.A. Bloomquist, The colorimetric determination of zirconium in plutonium-uranium-‘fissium’ alloys, Talanta, 6, 100, (1960).

 

11.          K.L. Cheng, Analytical applications of xylenol orange—I: Determination of traces of zirconium, Talanta, 2, 61-66 (1959).

 

12.          H. Faghihian, M. Kabiri-Tadi, Removal of zirconium from aqueous solution by modified clinoptilolite, J. Hazard. Mater. 178, 66–73 (2010).

 

13.          A. Merceille, et al. The sorption behaviour of synthetic sodium nonatitanate and zeolite A for removing radioactive strontium from aqueous wastes, Sep. Purif. Technol. 96, 81-88 (2012).

 

14.          H. Faghihian, et al. Preparation of a novel PAN–zeolite nanocomposite for removal of Cs+ and Sr2+ from aqueous solutions: Kinetic, equilibrium, and thermodynamic studies, Chem. Engin. J., 222, 41 (2013).

 

15.          A. Nilchi, et al. Evaluation of PAN-based manganese dioxide composite for the sorptive removal of cesium-137 from aqueous solutions, Appl. Radiat. Isot. , 70, 369 (2012).

 

16.          F. Sebesta, J. Johan, An overview of the development, Testing, and Application of composite Absorbers, Los Alamos National Laboratory, Report NO: LA-12875-MS, (1995).

 

17.          A.R. Nezamzadeh-Ejhieh, S. Tavakoli-Ghinani, Effect of a nano-sized natural clinoptilolite modified by the hexadecyltrimethyl ammonium surfactant on cephalexin drug delivery, Comptes Rendus Chimie, 17, 49–61 (2014).

 

18.          M.M.J. Treacy, J.B. Higgins, Collection of Simulated XRD Powder Patterns for Zeolites, Elsevier, Amsterdam, (2007).

 

19.          H. Tanaka, et al. Structure and formation process of (K, Na)-clinoptilolite, Mater. Res. Bull. 38(4), 713-722 (2003).

 

20.          R. Eslami Farsani, et al. FT-IR study of stabilized PAN fibers for fabrication of carbon fibers, World Academy of Sci. Eng. Technol., 50, 430-433 (2009).

 

21.          H. Faghihian, N. Godazandeha, Synthesis of nano crystalline zeolite Y from bentonite, J Porous Mater. 16, 331-335 (2009).

 

22.          A. Nilchi, et al. The application and properties of composite sorbents of inorganic ion exchangers and polyacrylonitrile binding matrix, J. Hazard. Mater. 37(3), 1271-1276 (2006).

 

23.          R.E. Connick, W.H. Reas, The Hydrolysis and Polymerization of Zirconium in Perchloric Acid, J. Am. Chem. Soc., 73, 1171 (1951).

 

24.          R.E. Connick, W.H. Mcvey, The aqueous chemistry of Zr, J. Am. Chem. Soc. 71, 3182-3191 (1949).

 

25.          C. Ekberg, et al. Studies on the hydrolytic behavior of zirconium(IV), J. Solution Chem. 33, 47 (2004).

 

26.          J.J. Tulock, G.J. Blanchard, Investigating Hydrolytic Polymerization of Aqueous Zirconium Ions Using the Fluorescent Probe Pyrenecarboxylic Acid, J. Phys. Chem. B. 106, 3568-3575 (2002).

 

27.          C. Walther, et al. Bergmann, Investigation of polynuclear Zr-hydroxide complexes by nano- electrospray mass-spectrometry combined with XAFS, Anal. Bioanal. Chem. 388, 409-431 (2007).

 

28.          S.K. Milonjić, Dj.M. Čokeša, R.V. Stevanović, Dynamic adsorption of uranium (VI) and zirconium(IV) on silica gel, J. Radioanal. Nucl. Chem., 158, 79-90 (1992).

 

29.          I. Langmuir, The Adsorption of Gases on Plane Surfaces of Glass, Mica and Platinum, J. Am. Chem. Soc, 40, 1361-1403 (1918).

 

30.          Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process Biochem, 34(5), 451-461 (1999).

 

31.          F. Rouquerol, J. Rouquerol, K.S.W. Sing, Adsorption by Powders and Porous Solids: Principles, Methodology, and Applications, Academic Press. San Diego, (1999).

 

32.          V.J. Inglezakis, S.G. Poulopoulos, Adsorption, Ion Exchange and Catalysis: Design of Operations and Environmental Applications, 1st ed., Elsevier, Amsterdam; Boston, (2006).

 

33.          W.J. Thomas, B.D. Crittenden, Adsorption Technology and Design; Butterworth- Heinemann: Oxford, Boston, (1998).

 

34.          H. Freundlich, Over the adsorption in solution, Z. Phys. Chem, 57, 384-470 (1906).

 

35.          M.M. Dubinin, L.V. Radushkevich, The equation of the characteristic curve of activated charcoal, Proc. Acad. Sci. USSR Phys., Chem. Sect., 55, 331-337 (1947).

Keywords

Clinoptilolite-polyacrylonitrile nano composite
Zirconium
Kinetic Parameters
Thermodynamic Parameters
Adsorption Isotherm
Recovery
1.             H. Faghihian, M. Iravani, M. Moayed, Application of PAN‐NaY Composite for CS+ and SR2+ Adsorption: Kinetic and Thermodynamic Studies, Environ. Prog. Sustain. Energy, 34, 999 (2015).
 
2.             M. Ghaemi, M. Torab-Mostaedi, M. Ghannadi-Maragheh, Characterizations of strontium (II) and barium (II) adsorption from aqueous solutions using dolomite powder, J. Hazard. Mater. 190, 916-921 (2011).
 
3.             Y.Q. Zhang, et al. Selective separation behavior of silica gel for zirconium in simulated high level radioactive liquid waste, J. Radioanal. Nucl. Chem, 247(1), 205-208 (2001).
 
4.             Q. Liang, H. Jing, D.C. Gregoire, Determination of trace elements in granites by inductively coupled plasma mass spectrometry, Talanta, 51 (3), 507-513 (2000).
 
5.             T. Onishi, S. Koyama, H. Mimura, Removal of zirconium from spent fuel solution by alginate gel polymer, Progress in Nuclear Energy, 82, 69-73 (2015).
 
6.             L.H.J. Lajunen, P. Peramaki, Spectrochemical Analysis by Atomic Absorption and Emission, Royal Society of Chemistry: Cambridge, (2004).
 
7.             J. Startý, J. Ruzicka, Metal chelate exchange in the organic phase—I: Theory: application in spectrophotometry and complex chemistry, Talanta, 14(8), 909-920 (1967).
 
8.             G.A. Welford, E.L. Chiotis, R.S. Morse, Submicroanalysis by Radiochromatography, Anal. Chem., 36 (12), 2350 (1964).
 
9.             B.A. Thompson, B.M. Strause, M.B. Leboeuf, Gamma Spectrometric and Radiochemical Analysis for Impurities in Ultrapure Silicon, Anal. Chem., 30, 1023-1027, (1958).
 
10.          R.F. Buchanan, J.P. Hughes, C.A.A. Bloomquist, The colorimetric determination of zirconium in plutonium-uranium-‘fissium’ alloys, Talanta, 6, 100, (1960).
 
11.          K.L. Cheng, Analytical applications of xylenol orange—I: Determination of traces of zirconium, Talanta, 2, 61-66 (1959).
 
12.          H. Faghihian, M. Kabiri-Tadi, Removal of zirconium from aqueous solution by modified clinoptilolite, J. Hazard. Mater. 178, 66–73 (2010).
 
13.          A. Merceille, et al. The sorption behaviour of synthetic sodium nonatitanate and zeolite A for removing radioactive strontium from aqueous wastes, Sep. Purif. Technol. 96, 81-88 (2012).
 
14.          H. Faghihian, et al. Preparation of a novel PAN–zeolite nanocomposite for removal of Cs+ and Sr2+ from aqueous solutions: Kinetic, equilibrium, and thermodynamic studies, Chem. Engin. J., 222, 41 (2013).
 
15.          A. Nilchi, et al. Evaluation of PAN-based manganese dioxide composite for the sorptive removal of cesium-137 from aqueous solutions, Appl. Radiat. Isot. , 70, 369 (2012).
 
16.          F. Sebesta, J. Johan, An overview of the development, Testing, and Application of composite Absorbers, Los Alamos National Laboratory, Report NO: LA-12875-MS, (1995).
 
17.          A.R. Nezamzadeh-Ejhieh, S. Tavakoli-Ghinani, Effect of a nano-sized natural clinoptilolite modified by the hexadecyltrimethyl ammonium surfactant on cephalexin drug delivery, Comptes Rendus Chimie, 17, 49–61 (2014).
 
18.          M.M.J. Treacy, J.B. Higgins, Collection of Simulated XRD Powder Patterns for Zeolites, Elsevier, Amsterdam, (2007).
 
19.          H. Tanaka, et al. Structure and formation process of (K, Na)-clinoptilolite, Mater. Res. Bull. 38(4), 713-722 (2003).
 
20.          R. Eslami Farsani, et al. FT-IR study of stabilized PAN fibers for fabrication of carbon fibers, World Academy of Sci. Eng. Technol., 50, 430-433 (2009).
 
21.          H. Faghihian, N. Godazandeha, Synthesis of nano crystalline zeolite Y from bentonite, J Porous Mater. 16, 331-335 (2009).
 
22.          A. Nilchi, et al. The application and properties of composite sorbents of inorganic ion exchangers and polyacrylonitrile binding matrix, J. Hazard. Mater. 37(3), 1271-1276 (2006).
 
23.          R.E. Connick, W.H. Reas, The Hydrolysis and Polymerization of Zirconium in Perchloric Acid, J. Am. Chem. Soc., 73, 1171 (1951).
 
24.          R.E. Connick, W.H. Mcvey, The aqueous chemistry of Zr, J. Am. Chem. Soc. 71, 3182-3191 (1949).
 
25.          C. Ekberg, et al. Studies on the hydrolytic behavior of zirconium(IV), J. Solution Chem. 33, 47 (2004).
 
26.          J.J. Tulock, G.J. Blanchard, Investigating Hydrolytic Polymerization of Aqueous Zirconium Ions Using the Fluorescent Probe Pyrenecarboxylic Acid, J. Phys. Chem. B. 106, 3568-3575 (2002).
 
27.          C. Walther, et al. Bergmann, Investigation of polynuclear Zr-hydroxide complexes by nano- electrospray mass-spectrometry combined with XAFS, Anal. Bioanal. Chem. 388, 409-431 (2007).
 
28.          S.K. Milonjić, Dj.M. Čokeša, R.V. Stevanović, Dynamic adsorption of uranium (VI) and zirconium(IV) on silica gel, J. Radioanal. Nucl. Chem., 158, 79-90 (1992).
 
29.          I. Langmuir, The Adsorption of Gases on Plane Surfaces of Glass, Mica and Platinum, J. Am. Chem. Soc, 40, 1361-1403 (1918).
 
30.          Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process Biochem, 34(5), 451-461 (1999).
 
31.          F. Rouquerol, J. Rouquerol, K.S.W. Sing, Adsorption by Powders and Porous Solids: Principles, Methodology, and Applications, Academic Press. San Diego, (1999).
 
32.          V.J. Inglezakis, S.G. Poulopoulos, Adsorption, Ion Exchange and Catalysis: Design of Operations and Environmental Applications, 1st ed., Elsevier, Amsterdam; Boston, (2006).
 
33.          W.J. Thomas, B.D. Crittenden, Adsorption Technology and Design; Butterworth- Heinemann: Oxford, Boston, (1998).
 
34.          H. Freundlich, Over the adsorption in solution, Z. Phys. Chem, 57, 384-470 (1906).
 
35.          M.M. Dubinin, L.V. Radushkevich, The equation of the characteristic curve of activated charcoal, Proc. Acad. Sci. USSR Phys., Chem. Sect., 55, 331-337 (1947).

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