INVESTIGATION OF THERMAL AND STRUCTURAL PROPERTIES OF NITRIC, HYDROCHLORIC AND SULPHURIC ACID-TREATED ZEOLITE

Yıl 2019, Cilt: 20 , 114 - 119, 16.12.2019

Meryem Akbelen Çağatay Ezber

https://doi.org/10.18038/estubtda.647910

Öz

 

In this study, in order to
consider the effect of the hydrochloric acid (HCl), nitric acid (HNO₃)
and sulphuric acid (H₂SO₄) treatments on
thermal and structural properties, zeolite was modified with 1 M
acid solutions at 70 ^oC during 4 h using batch method. The
structural and thermal properties of zeolites were studied by X-ray diffraction
(XRD), X-ray fluorescence (XRF), thermogravimetric analysis (TG), differential
thermogravimetric analysis (DTG) and differential thermal analysis (DTA). Quantitative
XRD analysis show that the natural zeolite mainly consists of mordenite and
clinoptilolite with varying amounts of quartz, feldspar and clay mineral. TG-DTG
and DTA curves of all zeolite samples were obtained in the temperature range
between 30 and 1000 ^oC. Based on the TG results, the
total mass losses for all acid-treated samples (8.51-8.44 %) are less than that
of the natural (Z) sample (10.14 %).  SiO₂/
Al₂O₃ ratio of the natural zeolite sample (Z) increased
from 5.6 to 9.8, 9.7 and 8.8 in the Z-N, Z-H and Z-S samples, respectively,
indicating the removal of the significant amount of aluminum from the zeolite
structure. 

Anahtar Kelimeler

Natural zeolite, Clinoptilolite, Mordenite, XRD, XRF, TGA-DTG-DTA

Kaynakça

• [1] Breck DW. Zeolite Molecular Sieves. New York, NY, USA: John Wiley and Sons, 1974.
• [2] Gottardi G, Galli E. Natural Zeolites, Berlin: Springer-Verlag, 1985.
• [3] Yang RT. Adsorbents. New York: Wiley, 2003.
• [4] Meier WM. The crystal structure of mordenite (ptilolite), Z. Kristallogr. 1961, 115, 439-450.
• [5] Baerlocher CH, Meier WM, Olson DH. Atlas of Zeolite Framework Types. 5th ed., Amsterdam, the Netherlands: Elsevier, 2001.
• [6] Misaelides P, Godelitsas A, Link F, Baumann H. Application of the 27Al(p, γ) 28Si nuclear reaction to the characterization of the near-surface layers of acid-treated HEU-type zeolite crystals. Microporous Mesoporous Mater 1996; 6: 37–42.
• [7] Hernandez MA, Petranovskii V, Avalos M, Portillo R, Rojas F, Lara VH. Influence of the Si/Al framework ratio on the microporosity of dealuminated mordenite as determined from N2 adsorption. Sep Sci Technol 2006; 41(9); 1907–1925.
• [8] Korkuna O, Leboda R, Skubiszewska-Zeiba J, Vrublevska T, Gunko VM, Ryczkowski J. Structural and physicochemical properties of natural zeolites: clinoptilolite and mordenite. Microporous Mesoporous Mater 2006; 87: 243–254
• [9] Elaiopoulos K, Perraki Th, Grigoropoulou E. Mineralogical study and porosimetry measurements of zeolites from Scaloma area, Thrace, Greece. Microporous Mesoporous Mater 2008; 112: 441-449.
• [10] Elaiopoulos K, Perraki Th, Grigoropoulou E. Monitoring the effect of hydrothermal treatments on the structure of a natural zeolite through a combined XRD, FTIR, SEM and N2-porosimetry analysis. Microporous Mesoporous Mater 2010; 134: 29-43.
• [11] Garcia-Basabe Y, Rodriguez-Iznaga I, de Menorval L, Llewellyn P, Maurin G, Lewisf DW, Binionsf R, Autieg MA, Ruiz-Salvadora R. Step-wise dealumination of natural clinoptilolite: structural and physicochemical characterization. Microporous Mesoporous Mater 2010; 135(1–3): 187–196.
• [12] Ates A, Hardacre C. The effect of various treatment conditions on natural zeolites: Ion exchange, acidic, thermal and steam treatments, J Colloid Interf Sci 2012; 372: 130-140.[13] Mansouri N, Rikhtegar N, Panahi HA, Atabi F, Shahraki BK. Porosity, characterization and structural properties of natural zeolite – clinoptilolite – as a sorbent. Environment Protection Engineering 2013; 39: 139–152.
• [14] Xu W, Li LY, Grace JR. Dealumination of clinoptilolite and its effect on zinc removal from acid rock drainage. Chemosphere 2014; 111: 427–433.
• [15] Lisa EB, Maria GJ. The effect of acid treatment on the reactivity of natural zeolites used as supplementary cementitious materials. Cement Concrete Res 2016; 79: 185-193.[16] Wang C, Cao L, Huang J. Influences of acid and heat treatments on the structure and water vapor adsorption property of natural zeolite. Surf Interface Anal 2017; 49: 1249–1255.
• [17] Ateş A. Effect of alkali-treatment on the characteristics of natural zeolites with different compositions. J Colloid Interface Sci 2018; 523: 266–281.
• [18] Abatal M, Córdova Quiroz Atl V, Olguín MT, Vázquez-Olmos AR, Vargas J, Anguebes-Franseschi F, Giácoman-Vallejos G. Sorption of Pb(II) from aqueous solutions by Acid-Modified Clinoptilolite-Rich Tuffs with Different Si/Al Ratios. Appl Sci 2019; 9: 2415.
• [19] Stocker K, Ellersdorfer M, Lechleitner A, Lubensky, J.; Raith JR. Impact of concentrated acid, base and salt pretreatments on the characteristics of natural clinoptilolite and its ammonium uptake from model solution and real effluents. Microporous Mesoporous Mat. 2019; 288: 109553.
• [20] Wang C, Leng S, Guo H, Cao L, Huang J. Acid and alkali treatments for regulation of hydrophilicity/hydrophobicity of natural zeolite. Appl Surf Sci 2019; 478: 319–326.
• [21] Esenli F. Natural zeolite reserves, mining, production, and market situation. In: National Zeolite Symposium; 2 July 2002; Tubitak-MAM, Gebze, Kocaeli (in Turkish).
• [22] Barrer RM, Makki MB. Molecular Sieve Sorbents from Clinoptilolite. Canadian J Chem 1964; (42): 1481-1487.
• [23] Moore DM, Reynolds Jr RC. X-ray Diffraction and the Identification and Analysis of Clay Minerals, 2nd edn., New York: Oxford University Press, 1997.