Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34

AUSTRALIAN JOURNAL OF BASIC AND APPLIED SCIENCES

ISSN:1991-8178 EISSN: 2309-8414 Journal home page: www.ajbasweb.com

Synthesis of Mesoporous Mordenite Zeolite by Different Natural Raw Materials

1Heman Smail, 2Kafia Shareef, 3Zainab Ramli

1Heman Abdulqadr Smail, Ph.D. Student, Chemistry, Salahaddine University, Erbil, Iraq, 2Kafia Mawlood Shareef, Professor, Clinical Biochemistry, College of Health Sciences, Erbil, Iraq, 3Zainab Hussein Ramli, Assist. Professor, Chemistry, Universiti Technologi Malaysia, Skudai, Johor, Malaysia,

Address For Correspondence: Heman Abdulqadr Smail, Salahaddin University, Chemistry Department, 44002 SUH Kirkuk Road, Erbil, Iraq.

ARTICLE INFO ABSTRACT Article history: Mordenite (Si/Al = 12.26) was hydrothermally synthesized from locally available low- Received 18 September 2016 cost materials using (Sunflower husk, Seed husk, Popcorn waste and chert rock) as a Accepted 1 January 2017 source of extracted Silica (SiO2) without the addition of a templating agent, seed Available online 16 January 2017 powder, structure-directing agent, and additives. Chert rock is the best-extracted silica source that can be used in synthesizing mesoporous Mordenite Zeolite by this method, since (Sunflower husk, Seed husk and Popcorn waste) were not obtained a significant Keywords: amount of silica. The starting material in the reaction temperature 25 ± 2°C for 72 h. Chert rock, hydrothermal The synthesized zeolites were characterized by Fourier Transform Infrared (FTIR) crystallization, Mordenite, Synthesis spectroscopy. The results obtained using X-ray diffraction (XRD) show moderate Zeolite. average crystal size of 26.65nm and confirm the formation of mordenite zeolite. X-ray Fluorescence (XRF) used to determine the Si/Al ratio and the result also confirmed the formation of mordenite zeolite. Field Emission Scanning Electron Microscopy (FE- SEM) was exploited to find out the morphology of the zeolite product and the result displayed a mixture of multi-faced spherules crystal with an ice hockey shape with different particle diameter along with round amorphous particles. The average pore size, pore volume and surface area were determined by Brunauer-Emmett and Teller (BET) method with values of 26.30 nm, 0.28 mL.g-1and 254.38m2.g-1 respectively. Finally, Transmission Electron Microscopy (TEM) was used to find the average crystal size and shape of zeolite, showing 37.82 nm of its average crystal size. The results verified that mordenite zeolites obtained from the hydrothermal condition, present a good zeolitic property and then can be suitable for using in adsorption ion exchange and catalysis experiments. The properties of zeolite materials formed are strongly depended upon the composition and the type of raw materials used.

INTRODUCTION

Zeolites are microporous crystalline aluminosilicates, chemically similar to clay minerals, but differing in their well-defined three-dimensional microporous structure. Silicon, aluminum, and oxygen are arranged in a - - regular structure of [SiO4] and [AlO4] tetrahedral units that form a framework with regular pores form of channels, tunnels, or cavities of about 0.1-2 nm diameter running through the material (Zaarour et al., 2014). Zeolites have been used as ion-exchange and molecular sieves in the separation and removal of gasses and solvents. Also, zeolites have the ability to act as a catalyst for chemical reactions which take place with in the internal cavities (Pal and Bhaumik, 2013). An important class of the reactions is that catalyzed by hydrogen- exchanged zeolites, whose framework-bound protons give rise to very high acidity. Therefore this property, zeolites have been used as a catalyst in petro chemistry and fine chemical industry because of their high surface

Open Access Journal Published BY AENSI Publication © 2017 AENSI Publisher All rights reserved This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/

To Cite This Article: Heman Smail, Kafia Shareef, Zainab Ramli., Synthesis of Mesoporous Mordenite Zeolite by Different Natural Raw Materials. Aust. J. Basic & Appl. Sci., 11(1): 27-34, 2017

28 Heman Smail et al, 2017 Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34 area, greater adsorption capacity, high hydrothermal and thermal stabilities, the strong acid sites within their defined micropores, and their shape selectivity in catalysis (Jin et al., 2008). For many catalytic applications, the main drawback of zeolites is their intricate pore and channel systems in the molecular size ranging from 0.3 to 1.5nm. Thus, large molecules cannot react effectively over these microporous materials because of the limitation of their small pore sizes (Huang et al., 1995). To solve the diffusion problems of guest species in zeolites, mesoporous materials with adjustable larger pore sizes, such as MCM-41 and SBA-15, have been successively invented (Qin et al., 2013). The mesoporous material, as defined by IUPAC nomenclature, is a material with the pore of free diameters in the range of 2-50 nm (Liu et al., 2008). The technological progress and modern scientific resulted in the rapid growth of industry and agriculture is accompanied by involvement in the economic diffusion of non-traditional types of mineral raw materials, one of which is zeolites (Barrer, 1982). It is no secret that the specific crystal structure of zeolite determines the number of more valuable properties, such as thermal stability, adsorption, catalytic activity, acidity, cations exchange and molecular sieves; zeolites have important applications in refining processes at the petrochemical industry, as well as gas separation, purification water at mining industry and environmental catalysis (Brek, 1976). The zeolite obtaining for drying natural gas, purification of gas and liquid industrial waste from environmentally harmful components, increasing the productivity of some branches of agriculture (animal husbandry, aviculture, crop, and so on) is of particularly important. The rapidly growing demand for zeolites necessitated their production (Мanafov et al., 2015).

Eeperimental And Method: Materials: Chert rock, Sulfuric acid (H2SO4) (GCC), pellets of sodium hydroxide (NaOH) (Aldrich), Sodium aluminate (NaAlO2) (FLUKA Company), pH meter (HANA Instruments pH 211 Microprocessor pH meter), Centrifuge (Hermle Z200A) and distilled water were used as the starting materials in the initial mixture for the synthesis of zeolite mordenite. The silica source used for the experiments was a chert rock obtained from Erbil- Iraq.

Silica Extraction: The procedure was followed to obtain silica from chert rock. The raw material was thoroughly washed with distilled water, dried at 110 ºC for 12 h and calcined at 800ºC for 4 h. A mixture of chert rock (10.03 g) and (5M) NaOH solution was stirred, at 600 rounds per minute (rpm) for (30 min), in a beaker. A filtered was the solution through Whatman No. 41 filter paper, and the residue was washed with 20 ml boiled distilled water. The filtrate and washings were allowed to cool at room temperature, and the solution pH was adjusted to pH 7.0 with (2.5M) H2SO4 at constant stirring at 600rpm. A soft white gel was formed and aged for 6 h, then washed by vacuum filtration then dried at 110ºC for 12 h (Abdullahi et al., 2013).

Synthesis of zeolite mordenite: Zeolite mordenite was synthesized from silica obtained from the selected raw materials, and their quantity was calculated based on their chemical composition according to their XRF analysis. Typically, 38. 90 g of NaOH was dissolved in 249.3 ml of water and then divided into two equal portions. In one portion, 5.56 g of extracted silica from the rock was completely dissolved. To other portion 10.19 g of NaAlO2 was added to prepare a clear aluminate solution. Then the silicate solution was slowly poured into the aluminate solution with vigorous stirring, which resulted in a clear homogenous solution. The resultant mixture was stored in an oil bath at room temperature T =25 ± 2°C, in a sealed poly tetra fluoro ethylene(PTFE) bottle under steering at 250 rpm for 3 days at pH 14. Then the solid product was separated by centrifugation (14000 rpm, 30 min) then washed more times by distilled water, until the pH value dropped to 8.69 and dried at 110°C overnight (Zahra and Habibollah, 2011).

Characterizations: Characterization of the synthesized zeolite sample was carried out by X-Ray Diffractometer type Siemens D5000 (XRD) with Bragg-Brentano geometry and Ni-filtered Cu Kα radiation (λ=0.1541° nm) at 40kv and current 30mA. The zeolite sample was mounted on the sample holder then was scanned in the range degree of 2휃 to the range of 5-50° with the step size of 0.05° in order to confirm the formation of mordenite phase (Harding, 2009). The presence of tetrahedral TO4 (T = Si, Al) bonding and formation of zeolite was determined using (FTIR), type Shimadzu 8400s (Ladavos et al., 2012). The spectrum was elucidated for zeolite framework -1 structure at wavenumbers between 400 and 4000 cm . The TO4 band positions of tetrahedral for zeolite framework are assigned according to the previous work (Yao et al., 2008). The (BET) method was used to determine the surface area, total pore volume, and average pore size of samples (Harding, 2009). The BET surface areas of materials were calculated from the adsorption branch of the isotherm using the BET equation (Kimura et al., 2012). Pore size distribution was determined by using the Barrett-Joyner-Halenda (BJH) method.

29 Heman Smail et al, 2017 Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34

The surface area of the samples was conducted by Micromeritics (3FLEX Surface characterization) analyzer. An amount of 0.1-0.2g of the sample was weighed and heated at 350°C, ramp rate 10°C/min for 240 min to dehydrate the sample zeolite. The zeolite sample was removed quickly to the sample station in the nitrogen adsorption analysis in which the analysis was fully done automatically by the instrument (Jaenicke et al., 2000). The surface area and pore distribution were obtained from the software of the instrument (Fujiwara et al., 2011). The morphology of the zeolite sample was determined by using FE-SEM. Samples were coated with Pt powder at 5.0KV with 100.000 time magnification (Enterrĺía et al., 2014). TEM images were taken on a JEM-2100 Electron Microscope JEOL with accelerating voltage of 160 kV to investigate the fine structure, morphology and particle size. XRF type Oxford Instrument X-Supreme 8000.

RESULT AND DISCUSSION

The chemical composition of mordenite zeolite synthesized by utilization of silica extracted from the selected raw materials was summarized in Table 1. Data in Table 2. Represents the type of zeolite mordenite obtained from chert rock source of silica that identified according to their silicon to aluminum ratio (Haoyu et al., 2001). The BET results for synthesized mordenite zeolite using rock as silica source used in this study. The larger surface area, higher pore volume and average pore size were attributed to the presence of the highly mesoporous structures in the synthesized zeolite sample summarized in Table 3.

FTIR spectrophotometer: In Fig 1, the band at 463cm-1 is related to the T–O–T bending of vibration mode (T), (Seyed et al., -1 2013).The band around 515cm is related to bending vibration of the SiO4 group. The stretching vibration of SiO4 is shifted towards lower frequency indicating that the presence of the internal Si-O∙∙∙HO-Si bonds. The bands around 695 and 778cm-1 stretching modes involving motions primarily associated with the T-atoms. Or described as symmetric modes (O-T-O) are assigned in the region of 800 and 880 cm-1 (Byrappa and Suresh, 2007). The band around 1086-1180cm-1 are due to the Si-O-Si asymmetric stretching vibration and asymmetric -1 stretching of SiO4 tetrahedra. While the bands around 1620cm resulted due to bending vibration of H-OH. This band was present even in sintered samples because water molecules were unable to escape from the silica matrix. The band is around 3440cm-1 are due to the stretching vibration of the O-H bond from the silanol groups (Si-OH) and is due to the adsorbed water molecules on the silica surface. The bands at 3695cm-1 are related to the -OH stretching modes as well as Si-OH and occluded OH-groups in the zeolite surface (Atsuo et al., 2015).

XRD Analysis: Fig 2, illustrates the XRD patterns of the synthesized zeolite mordenite, from chert rock XRD phase of mordenite is found to match with the show peaks at 2θ =6.51, 9.77, 18.07, 20.34, 26.14, 28.89, 30.39, 37.00, 38.92, 39.75, 40.55, 41.90, 42.62, 44.68, 46.94, 47.98, 48.85 and 49.59. These peaks are characteristic for mordenite zeolite, these peaks correspond to the planes [110], [200], [131], [041], [060], [441], [531], [711], [133], [570], [480], [423], [082], [063], [911], [173], [114] and [204]. It can It can be seen from Fig 1, that the synthesized sample showed the formation of mordenite phase (Treacy and Higgins, 2001). The average crystal size was calculated using Scherrer’s equation (Treacy et al., 1996). Bλ 푑 = (1) β COS θ

Where d is average crystal size (nm), B is the Scherrer’s constant (0.9), λ is the wavelength of the X-rays (nm), and θ is the value of the Bragg angle (i.e. the angle of the peak maximum). β is the full width at half- maximum (FWHM) of the broad peak after correction for intrinsic instrumental line broadening and must be in radians.

FE-SEM Analysis: FE-SEM micrograph of the studied samples showed the formation of twinned and intergrown lath-shape (slander elongated) crystal. Furthermore, a small portion of crystal cluster with a flaky habit is also depicted in the micrograph (Sang et al., 2004). FE-SEM images in Fig 3, for synthesized zeolite type mordenite shows that the most crystals formed as plates. Flat and prismatic crystals observed due to the high concentration of silica, the solid product contained a mixture of multi-faced spherules crystal with an ice hockey shape with different particle diameter along with round amorphous particles (Kim and Ahn, 1991). No physically isolated crystals or particles of the two phases were detected throughout the entire sample (Jyoti, 2010). The FE-SEM technique only shows the particulate structure of the mordenite in to confirm the presence of the nanometer spherical agglomerations seen with the FE-SEM technique. The FE-SEM analysis results for synthesized mordenite was confirmed by the results obtained from their FTIR, XRF, XRD, BET, TEM and literature.

30 Heman Smail et al, 2017 Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34

Surface Area and Pore Distribution Analysis: The sample was characterized using N2 sorption to determine their surface area and pore structure (Baerlocher et al., 2007). Depending mainly on the structure of solid, the adsorption of gasses and vapors gives rise to I-VI types of the isotherm. Fig 4(b) shows the isotherm, pore distribution and total pore volume for synthesized mordenite zeolite. It was found to BET surface area of zeolite mordenite have a Type IV isotherm it can be seen from Fig 4(a); at a relative pressure range of 0.45-0.99. According to the IUPAC classification (Sing, 1985). This kind of behavior is associated with mesoporous materials. Additionally, hysteresis loops are characteristics in mesoporous materials, and they are related with capillarity condensation. Also, it can be showed that the loop’s shape is classified as type H3 and this could be related to cylindrical pore channels. It was proven from the pore size distribution in Fig 4(b) which exhibited one narrow peak center at calculated 26.30 nm. Then it can be suggested that the average pore diameter of the mesoporous mordenite (Fan et al., 2008).

Transmission Electron Microscopy: Transmission Electron Microscopy is important technique Provides information about zeolite shape and crystal size (Cejka, 2003). Fig 5, TEM image shows the surface of synthesized mordenite zeolite, taken at 20 nm magnification also confirm the nature of the support, which is composed of ordered straight-channel, once again confirming the nature of the support used is this study; nanoparticles are arranged in an alternating fashion to form larger porous aggregates (Li et al., 2009). Sample zeolites, the TEM image of the channel that showed by an arrow was not clearly seen due to the strong agglomeration of the zeolite particle. This results in agreements with the FE-SEM image. The same information was reported in the literature (Hussein et al., 2015).

Table 1: XRF based chemical composition of the synthesized mordenite zeolites. Oxides (weight %) Zeolite Na2O MgO Al2O3 SiO2 P2O5 SO3 CaO MnO Fe2O3 H2O Mordenite 0.039 0.442 9.873 68.566 0.102 0.449 2.221 0.032 0.569 17.70

Table 2: The silicon to aluminum ratio and the type of the synthesized mordenite zeolites. Zeolite Sample specification Si / Al Ratio Type Isotypes Mordenite Chert rock 12.266 MOR Mordenite

Table 3: N2 adsorption-desorption for synthesized mordenite zeolite. BET Average crystal Average crystal Average pore size Zeolite surface area Pvb(mLg-1) size size* (nm) (m2 g-1) (nm)-TEM (nm)-XRD Mordenite 254.38 0.28 37.82 26.65 26.30 bTotal pore volume obtained at 푃/푃° = 0.99. *The crystal sizes were calculated by applying the Scherrer’s equation to the XRD reflections of [060] plane.

Fig. 1: FTIR Spectrum for synthesized mordenite zeolite

31 Heman Smail et al, 2017 Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34

Fig. 2: XRD Spectrum for (a) reference for mordenite (b) synthesized mordenite zeolite

Fig. 3: FE-SEM image for synthesized mordenite zeolite

32 Heman Smail et al, 2017 Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34

Fig. 4: (a) N2 sorption isotherm (b) Pore size distribution and pore volume for synthesized mordenite zeolite

Fig. 5: TEM image for synthesized mordenite zeolite

Conclusion: In conclusion, it can be said that the mesoporous Mordenite is able to be synthesized by using chert rock as a source of silica. Other types of wastes such as (Sunflower husk, Seed husk and Popcorn waste) that were used in this method do not contain a significant amount of silica. Chert rock is the best silica source that can be used in synthesizing mesoporous Mordenite Zeolite. Zeolite gives a big contribution to the world of chemistry by having wide applications especially as the catalyst. In many catalytic applications, the main lack of zeolites is their intricate pore and channel systems in the molecular size ranging from 0.3 to 1.5 nm which is a microporous size. It makes large molecules do not react effectively over these microporous materials because of the limitation of their small pore sizes. Therefore, to overcome this limitation of zeolite, the idea of having mesoporous material characteristic is desirable in order to improve the limitation of zeolite so that it can be used in wider applications by allowing large molecules react effectively over the mesoporous zeolite. The results for Nitrogen adsorption analysis revealed that the synthesized zeolite has the mesoporous structure with type IV

33 Heman Smail et al, 2017 Australian Journal of Basic and Applied Sciences, 11(1) January 2017, Pages: 27-34 isotherm and H3 hysteresis loop with an average pore size of 26.30 nm and high BET surface area. FE-SEM result exhibited flat and prismatic crystals observed due to the high concentration of silica; the solid product contained a mixture of multi-faced spherules crystal with an ice hockey shape with different particle diameter along with round amorphous particles. Furthermore, the synthesis of mesoporous mordenite zeolite was based on using natural raw materials such as chert rock as the best source of silica. Also, it should be pointed out that the mordenite zeolite was synthesized using local raw materials, without an addition of a templating agent, seed powder, structure-directing agent, and additives, which leads to a reduction of cost price desired product. This fact prompts us to evaluate the possibility of investigating the reactivity of chert rock as the raw material in a formation of zeolites and or zeolitic materials. Finally, utilization of chert rock obtains mordenite type of zeolite according to their silicon to aluminum ratio and XRD-results. The properties of zeolite materials formed are strongly depended upon the composition and the type of the raw material used. Implementation of the determined method allows extending the raw materials base, simplifying the synthesis and reducing the cost of powdery mordenite type zeolite and its available from Erbil-Iraq.

Future Work: There are many advantages of synthesizing mesoporous zeolite. Zeolite is well known as a molecular sieving. By having mesoporous zeolite that has a larger size of the pore, mesoporous zeolite will be able to separate larger molecules. Other than that, the mesoporous zeolite is also well known as a good catalyst in many catalytic processes. Therefore, by synthesizing mesoporous zeolite that has larger pore system, it will be able to perform a catalytic process on larger molecules. Moreover, rock that will be used as an excellent source of silica is inexpensive and nontoxic. Thus the synthetic process becomes a pollution-free. This type of zeolite is also suitable for using in adsorption ion exchange and catalysis experiments.

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