Controllable synthesis of NaP zeolite and its application in calcium adsorption

Abstract

functional performance of the different kinds of zeolites, many studies have been devoted to improving synthetic approaches to control crystal size, the size of the intracrystal-line pore/channel system and morphology of zeolites [5,6]. Among various types of zeolites, NaP (Na 6 [(AlO 2) 6 (SiO 2) 10 ]⋅15H 2 O) is one of the most interesting structured zeolite with two sets of intersecting channels: 0.31 nm × 0.44 nm and 0.26 nm × 0.49 nm. According to International Zeolite Association (IZA), this structure is called "Gismondine" (GIS) framework topology [7,8]. NaP zeo-lite offers the greatest promise for gas separation applications due to its small pore size [9,10], and is also useful for removal of toxic and radioactive waste species like Cs, Sr, Ba, Pb, U, heavy metals, and ammonium from wastewater, seawater potassium extraction and formation of environmental friendly detergent [11,12]. NaP zeolite can be synthesized from various precursor materials and various methods. It can be synthesized from: (i) clay at a crystallization temperature of 85ºC [13], (ii) sodium silicate solution [14], and (iii) high silicon fly ash of coal combustion at 120ºC for 4 h [15]. Among them the most common methods used for the synthesis of NaP ze-olite are the sol-gel technique, hydrothermal synthesis and microwave heating synthesis [1]. The NaP zeolite with different morphologies can offer many intriguing properties: places to store the guest molecules and to perform chemical reactions with selected-sized molecules. Thus, the NaP zeolite morphology and its important correlation with properties is the need of the recent research. In this work, we attempted the template free hydrother-mal synthesis of NaP under controlled conditions. Based on multiple paths that can be involved in the hydrothermal synthesis of NaP, optimization of crystallization conditions was adapted through variation of the following parameters: Na 2 O/SiO 2 and SiO 2 /Al 2 O 3 molar ratios, aging time and aging temperature. The characteristics of the synthesized gels NaP zeolite particles were prepared through a template-free hy-drothermal condition at 100ºC. Parameters like Na2O/SiO2 and SiO2/Al2O3 molar ratios, gel aging time and aging temperature were investigated for regulating the crystallization of the final product. The samples at different synthesis stages were characterized with N2 adsorption at −196ºC, field emission scanning electron microscopy (FE-SEM), temperature programmed desorption of ammonia adsorption, X-ray diffraction, ther-mogravimetric and differential scanning calorimetry analysis and Fourier transform infrared spectroscopy. The experimental results evidenced that a high ordering crystallinity of NaP zeolite was obtained at Na2O/SiO2 and SiO2/Al2O3 molar ratios of 1.10 and 1.40, respectively, and a temperature of 100°C for 4 days of aging. FE-SEM image exhibited polycrystalline aggregates of NaP zeolite with crystallite sizes ranging up to 5.04 μm with cactus/cabbage like structures. The quantitative analysis of the total number of acid sites was found to increase as Na2O increases. The NaP zeolite sample with a Na2O/SiO2 molar ratio of 1.13 exhibited a large fraction of the acid sites on its external surface, contrary to that synthesized with a relevant ratio of 1.10. The optimized NaP zeolite could be successfully bestowed with excellent sorption properties of Ca(II) in aqueous solution. The kinetic parameters for Ca(II) adsorption were thoroughly investigated.