THE EFFECTS OF ADDING 1 M NaOH, KOH AND HCl SOLUTION TO THE FRAMEWORK STRUCTURE OF NATURAL ZEOLITE

  MATERIALS SCIENCE and TECHNOLOGY

  Edited by Evvy Kartini et.al.

  

THE EFFECTS OF ADDING 1 M NaOH, KOH AND HCl SOLUTION

TO THE FRAMEWORK STRUCTURE OF NATURAL ZEOLITE

Supandi Suminta, Supardi and Parikin

  

Center for Nuclear Industry Materials Technology, National Nuclear Energy Agency

Kawasan Puspiptek Serpong Tangerang BANTEN

e-mail: ssupandi@gmail.com

  ABSTRACT

  Zeolite structures contain (-Si-O-Al-) linkages that form surface pores of uniform diameter and enclosed regular internal cavities and channels of discrete size and shapes. This, however, also depends on the chemical composition and crystal structure of the specific zeolite involved. The main purpose of this study is to investigate the changing of the structural parameters and increasing of cationic exchange and molecular seaving properties. Adding 1M NaOH, KOH and HCl solution to the natural Lampung zeolite built a Na-zeolite, K-zeolite and H-zeolite using ion exchange metods. An identification of the framework of mineral structure of Na-zeolite, K-zeolite and H-zeolite were carried out by Reitveld methods and Gaussian Fitting analysis. X-ray diffraction intensity of Na-zeolite, K-zeolite and H- zeolite were measured by an X-Ray Diffractometer (XRD) at PTBIN-BATAN Indonesia. The refinement of Clinoptilolite and Mordenite phases were carried out and the results of refinement shows that the Na-zeolit, K-zeolite and the control zeolit consisted of Clinoptilolite phase (space group C2/m HEU No.12, Bravais lattice is Base-Centered and crystal system is monoclinic), and the lattice parameters are a = 17,75(8) Å, b = 17,86(2) Å and c = 7,604(6) Å for Na-zeolite and a = 17,78(1) Å, b = 17,97(7) Å and c = 7,45(6) Å for K-zeolite. Fitting analysis was done to the Bragg peaks of diffraction pattern (raw data). The values of 2

  θ angle and FWHM for the Bragg reflections have decreased in comparison to the control zeolite. The Lampung zeolite are polycrystalline of clinoptilolite phase in monoclinic. The crystalline quality of Lampung zeolite significantly depends on substance and concentration of NaOH, KOH and HCl . The strain (

  η) of the CONTROL Zeolite, Na- zeolite, K-zeolite, and H-zeolite are 0.095, 0.085, 0.420 and 1.535 respectively. While the crystal size (D) are 62 nm, 71 nm, 102 nm, and 14 nm respectively. It is concluded that the chemical method process of exposing natural zeolite to base increases the crystal size, due to decreasing microstrain, while into acid decreases crystal size, due to increasing microstrain. Hence, The Lampung zeolite structure is damaged due to exposure to acid.

  

Keywords: X-ray diffraction, microstrain, clinoptilolite, Rietveld method, Gaussian Fitting

analysis

  INTRODUCTION

  The atomic structures of zeolites are based on three-dimensional frameworks of silica and alumina tetrahedral, that is, silicon or aluminum ions surrounded by four oxygen ions in a tetrahedral configuration. The oxygen is bonded to two adjacent silicon or aluminum ions, linking them together. Clusters of tetrahedral formed boxlike polyhedral units that are further

  Materials Science and Technology

  linked to build up the entire framework. In different zeolites the polyhedral units may be equidimensional, sheet like, or chainlike. The aluminosilicate framework of a zeolite has a negative charge, which is balanced by the cations housed in the cagelike cavities. Zeolites have much more open, less dense structures than other silicates; between 20 and 50 percent of the volume of a zeolite structure is voids. Silicates such as zeolites that have three- dimensional frameworks of tetrahedral are termed tectosilicates. Besides the zeolites, other tectosilicates include quartz and feldspars.

  Crystal structures of zeolites which are periodically ordered in 3 dimensions are ordered structures (regular crystalline solids). Statistically disordered structures show periodic ordering in dimension less than 3, i.e. 2, 1 or 0 dimensions. This phenomenon is also called stacking disorder of structurally Periodic Building Unit (PerBU)[1]. In this sense we exclude chemical disorder, e.g. different cation on a particular site, and dynamic disorder, e.g. rotational disorder of template molecules. We also exclude structural disorder within cavities of zeolite frameworks. Consequently, disordered structures are built from periodic 0- 1- 2- dimensional perBU’s which are built from smaller unit, e.g. translation, rotation. The relative orientation of neighboring PerBU’s can be described by stacking modes between the parallel aligned PerBU’s. The stacking mode contains the symmetry element which relates the PerBU’s to each other including lateral translation components given in fraction of the basis vectors of the invariant PerBU. Crystal structures built from PerBU’s are called end-member structures if periodic ordering is achieved in all three dimensions. Disordered structures are those where the stacking sequence of the PerBU deviates from periodic ordering up to statistic stacking sequences. All structures built from the same PerBu, ordered end-member structures and disordered and disordered intermediates belong to the same family of structure type.

  The objectives of these study are to determine the crystal structure phase, crystal size and micro-strain of Lampung zeolite with various chemical solution that carried by the natural zeolites to allow appropriate treatment and final utilization of natural zeolites.

EXPERIMENTAL METHOD

  ° Reflux of natural Lampung zeolite was carried out at 150 C for 6 hours with distilled water.

  The Na-Zeolite, K-Zeolite and H-Zeolite samples were prepared by using (10 ml/mn) of 1 M NaOH, KOH and HCl solution through the zeolite powder. The powder was placed inside a 1 Liter glass column during the procedure. Following the activation the zeolites was further

  °

  treated until pH reached neutrality. The powder was then dried through heating at 105 C. Step counting (0.02 step) of X-ray diffraction measurements were carried out to check the quality of the Na-Zeolite, K-Zeolite and H-Zeolite samples. X-ray diffraction measurements were performed for all zeolite samples by using a Philips instrument at PTBIN-BATAN Indonesia.

RESULTS AND DISCUSSION

  Figure 1 shows the X-ray diffraction pattern with three different chemical solutions and one as a control (1M NaOH, KOH and HCl and control). There was Bragg scattering peaks in the zeolite samples respectively plotting in the figure.

  The results of fitting analysis to the Bragg peaks in zeolit at four different chemical solution (Na-zeolite, K-zeolite, H-zeolite and M-zeolite) and four different peaks respectively are listed in Table 1 and 2. With adding different chemical solution, in general, the peak shifts into the lower angle respectively. The change is caused by adding chemical solution of the natural zeolite crystalline in the mono cation. The fitting data of analyzing patterns to the

  The Effects of Adding 1 M NaOH, KOH and HCl……

  Bragg peak in Na-zeolit, K-zeolit, H-zeolit and M-zeolite at three different chemical solutions and at three different peaks are listed in Tabel 1 and 2 and also Figure 1 and 2, respectively

  

Figure 1: X-ray diffraction pattern of Lampung Zeolite with four different chemical solution: HCl 1M (H-

zeolite), KOH 1M (K-zeolite), NaOH (Na-zeolite) and Control (M-zeolite)

Figure 2: X-ray diffraction patterns of Lampung Zeolite (raw data) with 4 different chemical solutions; HCl

  1M, KOH 1M, NaOH 1M and Control and Fitting analysis to the Bragg peaks. (up) Zoom, with range 2 θ : (9.2 - 11.0), (middle) Zoom, with range 2 θ : (10.5 -12.0), (bottom) Zoom, with range 2θ : (21.5-24.0).

• 14 1.535 Peak 2 - - Peak 3 0.2935 0.1995

  71

   

  D Cos 2 94 .

       Sin

  Clinoptilolite Crystal in the H-zeolite, K-zeolite, Na-zeolite and M-zeolite respectively were estimated through the Hall’s equation [2,3] which is expressed as:

  βCosθ and Sinθ on H-zeolite, K-zeolite, Na-zeolite and M- zeolite (Control) to calculate cryatal size (D) and microstrain ( η). The lattice strain of

  62 Table 2 gives data of

  AVG

  60 0.095 Peak 2 0.3154 0.1003 Peak 3 0.2734 0.1981

  55

  70

  71 M-zeolite (Control) Peak 1 0.2068 0.0896

  AVG

  78 0.420 Peak 2 0.2043 0.0999 Peak 3 0.1836 0.1974

  65

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  102 NaOH 1M Peak 1 0.3187 0.0884

  Peak 3 0.1435 0.1937 AVG

  98 110 100 0.185 Peak 2 0.1316 0.0970

  14 KOH 1M Peak 1 0.1815 0.0858

  AVG

  14

  Lampung Zeolit Peak βCosθ Sinθ D(nm) Strain ( η) HCl 1M Peak 1 1.0113 0.0897

  1 9,8497 4,92485 0,1822 (200) Peak 2 11,1310 5,5655 0,1322 (111) Peak 3 22,3440 11,1720 0,1463 (041) NaOH 1M Peak 1 10,1380 5,0690 0,3200 (200) Peak 2 11,4770 5,7385 0,2053 (111) Peak 3 22,7720 11,386 0,1873 (041) CONTROL Peak 1 10,2840 5,1420 0,2076 (200) Peak 2 11,5180 5,7590 0,3170 (111) Peak 3 22,8530 11,4265 0,2789 (041) Table 2: Data of crystal size (D) and microstrain of Lampung zeolite with various chemical solution.

  Peak 2 11,8330 5,9165 0,0254 (111) Peak 3 23,0130 11,5065 0,2995 (041) KOH 1M Peak

  2 θ θ FWHM ( β) - HCl 1M Peak 1 10,2950 5,1475 1,0154 (200)

  Lampung Zeolit Peak

  Table 1: Bragg peak position ( θ), and FWHM data of Lampung zeolite, with various Solution of HCl 1M, KOH 1M, NaOH 1M dan CONTROL

  Bragg reflections on the peak 1, peak 2 and peak 3 have decreased in comparison to the Control. These changes are caused by adding processes.

  Table 1 shows the data of Bragg reflection which demonstrates that for the materials of H-zeolite, K-zeolite, Na-zeolite and Control, the value of 2 θ angle and FWHM for the

  (1)

  The Effects of Adding 1 M NaOH, KOH and HCl……

  where β is the half-width of a given diffraction peak,  is the wavelength of X-ray used, η is a measure of the lattice strain[4,5],

  θ is the Bragg angles and D is the crystallite size. Figure 3 shows the relation between βCosθ and Sinθ for peak 1, peak 2 and peak 3 diffraction peaks of clinoptiloite phase in the Lampung zeolite on H-zeolite, K-zeolite, Na-zeolite and M-zeolite

  (Control).

  The values of lattice strain, η in Eq. (1), are obtained from the slopes of the plot. It is apparent that H-zeolite has larger lattice strain compared to the K-zeolite, Na-zeolite and M- zeolite. Such a large lattice strain of M-zeolite is caused by chemical procsses at the cavity of zeolite and zeolite structure is damaged due to exposure to acid. The crystallite size of K- zeolite, Na-zeolite H-zeolite and M-zeolite are estimated from the calculation of Hall’plots, i.e Eq. (1).

  The lattice strain, η value is large on HCl 1 M and decrease with NaOH 1M, KOH 1M and M-zeolite.

  η value are 0.095 (M-zeolite), 0.185 (KOH), 0.420 (NaOH) and 1.535 (HCl) respectively. While crystal size, D value is large about 102 nm on KOH 1M and decrease with HCL 1M, NaOH 1M and M-zeolit respectively. D values are 62 nm (M-zeolite), 71 nm (Na-zeolite), 102 nm (K-zeolite), and 14 nm (H-zeolite) respectively.

  

Figure 3: Hall’s plot for diffraction Bragg peaks of Lampung Zeolit at four different chemical solution, HCL

  1M (H-zeolite), KOH 1M (K-zeolite), NaOH 1M (Na-zeolite and Control (M-zeolite) CONCLUSION

  We have investigated the dependence of chemical solution (i.e. NaOH 1M, KOH 1M and HCl 1M ) on microstrain and particle size of Natural Zeolite from Lampung (Lampung Zeolite). The zeolite as Na-zeolite, K-zeolite and H-zeolite were prepared by chemical solution reaction and formed by ion exchange method. The Lampung zeolite are polycrystalline of clinoptilolite phase in monoclinic. The crystallinity of Lampung zeolite significantly depends on the substance and concentration of NaOH, KOH and HCl. The strain (

  η) of the CONTROL M-Zeolite, Na-zeolite, K-zeolite and H-zeolite are 0.095, 0.085, 0.420 and 1.535 respectively. While the crystal size (D) are 62 nm, 71 nm, 102 nm, and 14 nm respectively. It is concluded that the chemical method process of exposing natural zeolite to base increases the crystal size, due to decreasing microstrain, while exposure to acid decreases crystal size, due to increasing microstrain. Hence, The Lampung zeolite structure is damaged due to exposure to acid.

  Materials Science and Technology REFERENCES

  [1]. http://www.zeoinc.com/zeolite.shl, 1/6/2008 [2]. B.D. Cullity., and S.R. Stock, Elements of X-ray Diffraction, Third Edition, Prentice Hall, Upper Saddle River,New Jersey 07458, 2001.

  [3]. T.Sutomu Minami, Toshiharu Saito, and Masahiro Tatsumisago, Solid State Ionic, 86- 88, 415 (1996). [4]. M. Tatsumisago, A. Taniguchi and T. Minami, J. Am, Ceram.Sos., 76, 235 (1993).

  M. Tatsumisago, Y.Shinkuma, T. Saito, and T.Minami, Solid State Ionic, 50, 273 [5]. (1992).