Technologic Tests of Turkey-Gordes Zeolite Minerals

Natural zeolites are found at many points of the world in the form of minerals. As for Turkey, quite large volumes of zeolites reserves are available in the following regions: Ankara (Nallihan, Beypazari, Polatli etc.), Kütahya-Saphane, Manisa-Gördes, Manisa-Demirci, Izmir-Urla, Balıkesir-Bigadiç and Cappadocia. By means of the works carried out only at the field in BalikesirBigadiç region, one of the detected reserves in Turkey, it was understood that an easily workable potential around 500 million ton is available. According to the very limited observations made until today, it is stated that the total reserve in our country may be around 500 billion ton. In these regions, the types of clinoptilolite, hoylandit, chabazite, analcime and erionite from the zeolite minerals exist. Zeolites are widely used in many sectors such as energy, environment, construction, detergent, chemistry, medicine, mining, agriculture and livestock. Zeolites also provide great benefits when they are used especially in agriculture and livestock for the purpose of preventing environmental pollution threatening human being. In this study, zeolite sample taken from Manisa-Gördes region was used. Following the processes of crushing and sieving, zeolite sample was subjected to chemical analyses according to their grain thickness, microscopic examination, the analyses of XRD and Technological Tests (ceramic pre-technological reviews, value of oil absorption, whiteness measurements, examination of the zeolite sample as cat litter, determination of bleaching capability, porosity values) and their ore characteristics were determined. After the analyses, ferrous oxide, biotite, quartz, muscovite, feldspar, chlorite, non-zeolite silicates and metamorphic rock fragments have been found. This zeolite mineral with high mineral purity has been suggested to clear off all impurities via ore preparation and enrichment methods.


Introduction
Zeolite is a word meaning "Fusing Rock". It earned this name because of its ability to explode and disintegrate when it is heated. Zeolite was first discovered in 1856 by Swedish mineralogist Freiherr Axel Fredrick Cronstedt. Zeolites are a mineral group that is formed by the change of volcanic ash in aquatic environment millions of years ago, comprising alkali and alkaline-earth hydrated natural silicates. Zeolitization is a process in which feldspar and other aluminosilicates turn into zeolites. Zeolite minerals are in an aluminosilicate structure which is comprised of connected tetrahedral AlO 4 and SiO 4 via sharing oxygen atoms and can grow infinitely as a three dimensional web. Their structure is similar to honey combs or cages and includes alterable cations and water. Micro foramens between the units merge in micro windows and form one, two or three dimensional clearance systems and canals. The amount of clearance is between 20% and 50% of the total volume. These channels and cages are adequate for adsorbing molecules smaller than these channels and/or tunnels, so in this regard, zeolites are known as "molecular sieves" [1] [2] [3].
One of the main properties of zeolites is its canals (pores), which have a homogenous structure in crystal form. Zeolites have ion exchange, absorption, molecular sifting and catalytical effect mechanisms because of these [4] [5] [6] [7] [8]. Zeolite skeleton is formed by the open crystal cage wave formation of different shapes of SiO 4 and AlO 4 tetrahedras. Its micro canal structure is formed by its crystal cage structure, which contains canals on a molecular scale [6] [7].
There are more than 40 known minerals. The most important of these are clinoptilolite, heulandite and chabazite. With its chemical formula of (Na,K) 6 (Al 6 Si 30 O 72 )•20H 2 O, clinoptilolite's crystal system is monoclinic, and its competence in silicates class is 3.5 -4, and its specific gravity is 2.2. It is vitreous, neat, transparent or semi-transparent. It can be colourless, white, pink, yellow or have a reddish hue. It is resistant to heat. Its Si/Al mol ratio is 0.425/5.25. It is a resistant zeolite to acid (pH: 1. 5 -11). Its crystal clearance is 39%. Its most important feature is its canal shaped clearance structures. Its water, oil and gas absorption capacity is relatively high. Clinoptilolite is formed via the transformation of volcanic glass and tuff into crystal materials with the effect of heat. Volcanic rocks form with basalt, rhyolite and andesite and with borate minerals in deep seas as residuum.
Clinoptilolite and heulandite are very similar in terms of their crystal structure and they cannot be distinguished from each other, even in X-Ray images.
Both zeolite minerals are formed in a layered structure, tectosilicate sub class and their oxygen atoms are covered by silica or aluminium ions. Layers are formed by 8 -10 edged open rings and layers are piled together and form canals and clearance within the crystal. Canals work like a molecular sieve because of their ability to allow certain molecules and deny certain others according to O. Bilgin their sizes. Clinoptilolite's difference from heulandite is its relative richness of silica and the fact that it is more resistant to heat. For example, heulandite transforms to another phase which is named as heulandite B in 230˚C and becomes completely amorphous in 350˚C. Clinoptilolite retains its crystal formation up to 700˚C. It is heulandite if the (Na + K)/(Na + K + Mg + Ca) ratio is bigger than 0.5; otherwise it is clinoptilolite [9] [10]; or it is clinoptilolite if the (Na + K)/(Mg + Ca) ratio is bigger than 0.69; otherwise it is heulandite [11]. It is clinoptilolite if the Si/Al ratio per cell is bigger than 4; otherwise it is heulandite [12].
Manisa-Gordes zeolites are in the structure of potassium, calcium clinoptilotite in high thermal stability and have a specific gravity between 1.98 -2.18 g/cm 3 . Bulk density varies according to granule bulk between 0.693 -1.22 g/cm 3 . The specific surface area of Gordes zeolites is 40.80 m 2 /g. Gordes zeolites release their foramen water in 50˚C -90˚C, bound-water at 90˚C -320˚C, crystal water at 360˚C -770˚C and their structure begins to dissolve at 839˚C.
Thermal stability endures up to 1000˚C. The water absorption capacity of Gordes zeolites is between 15% -30%. Gordes zeolites have high thermal stability and their natural unit bulk weight is 1.36 g/cm 3

Geology of Manisa-Gordes Region
Turkey has one of the largest and richest reserves of zeolite in the world, including the Bigadic and Gordes reserves [11] [15]. Zeolite mineral formation is observed in nearly 2/3 of the tuffs in Miocene piles in the Manisa-Gordes region.   [16].
Experiments subject to this study are carried out upon the zeolite samples that were obtained from zeolite facilities still active in production in the Manisa-Gordes region. The Manisa-Gordes location map is illustrated in Figure 1. Belonging to these fields in the research study, zeolite was taken from this field according to the method. In addition zeolite, with its ion exchange, adsorption and catalyst properties, is known to be used as a filling material in paper production, for seeking uranium beds in mining, as a light component element and cement additive in construction, in water culture applications, powder detergent applications, as a defroster on highways and in many other industries such as medicine [17] [18] [19] [20] [21].

Applications Technologic Tests of Zeolite
According to the work performed in taking into consideration the firing position and the colors; the zeolite sample shows us that it is unsuitable for use in the ceramic industry. Ceramic pre technological reviews on a zeolite sample are presented in Table 2.  Because of the physical properties of the zeolite sample, the real density analysis could not be identified using device Accupyc Pycnometer 1330 Hc. In addition, water absorption tests could not be completed, due to the dispersion in water. The all of these results are presented in Table 3.
Determination of the original sample bleaching capability: After the sample was dried on 55˚C ± 5˚C until constant mass, it was ground to pass through the 200 mesh (74 micron) bottom sieve. 1 g of the sample was put into the tube, 20 ml of oil-benzene mixture was added, and it was shaken for 10 minutes. After 24 hours, the value of % T (permittivity) was read on a calorimeter and the equivalence of tonsil was determined.
Determination of the activated sample bleaching capability: After the sample was dried on 55˚C ± 5˚C until constant mass, it was ground to pass through the 200 mesh (74 mikron) bottom sieve. 100 ml of distilled water was placed in accordance beaker and 20 g of the sample was added. This mixture was then mixed thoroughly with begets and 12.5 ml, 98% concentrated H 2 SO 4 was added. It was kept for 1.5 hours on a hot plate at boiling point. After the boiling time, the sample was left for 24 hours. Afterwards, the sample under vacuum was filtered until there was no acid in permeate and left to dry. The sample in the form of a dried cake was ground again and the bleaching process was applied to the original sample again. Chemical analysis results of the sample are presented in Table   4.

X-Ray Analyses of the Zeolite Sample
The zeolite sample was subjected to X-Ray diffractometer studies. Which diffraction distribution corresponds to which 2θ was defined by the peaks in the continuous spectrum by the X-Ray diffractometer shoots. The DHKL distances and reflection intensities which corresponds to each 2θ that provides Bragg diffraction condition (nλ = 2dSinθ) were detected from catalogues. In order to define the phases that the peaks belong to, diffraction indexes created by American In the X-Ray studies defined according to the conditions above, zeolite has the same properties and includes both Heulandite and Clinoptilolite. In Table 5, the detected mineral structure according to the X-Ray analysis is provided. Heulandite properties are higher than Clinoptilolite in the zeolite sample. In addition, quartz, feldspar and biotite minerals were also detected with X-Ray.
The result of XRD analysis carried out between 2˚ -70˚ by a Philips PW 3710/1830 XRD analyser with a Cu X-ray tube is presented below in Figure 2.
There are zeolite group minerals (heulandite-clinoptiolite, very little analcime    by Olympus SZx16 type binocular microscope are presented below. Microscopic images of zeolite sample can be seen in Figures 3(a)-(e) Zeolite's binocular microscopic images, as can be seen in Figure 3(a), show the base surface under white clean zeolite minerals and partial biotite (mica) and ferrous oxide contamination can be observed (5×).

Microscopic Analysis of the Zeolite Sample
Zeolite's binocular microscopic images, as can be seen in Figure 3  observed gravimetrically under the R04 visuals of nearly 20% (1.5×). This event points out that the zeolite is contaminated. According to the usage areas, this type of zeolite can be selectively broken under 1 mm or 0.5 mm and converted to a cleaner product via enrichment according to density. Waste and side products that emerged after this enrichment process can also be used according to the consumption, for example in soil improvement.
Zeolite's binocular microscopic images in the grain size of −1.5 mm, as can be seen in Figure 3(c). is bated into the zeolite sample, it is seen and observed that quartz and ferrous oxide and other biotite-clamped grains are intensified because they are denser than zeolite, and if a clean process is performed among them, for example planar attraction, cleaner crystal quartz can be obtained clean crystal quartz can be obtained. These obtained quartzes can be used in the glass or ceramic sector. Images obtained by the microscopic analyses carried out on the thin sections prepared from a zeolite sample are presented in Figure 3(f). According to these images, the zeolite sample contains trace minerals such as biotite, metamorphic rock remnants, iron, quartz, plagioclase (feldspar), as seen in Figure 3(f).
In the microscopic analyses, the first degree of the softest zeolite minerals and clay show fine grain sized collapse, third degree quartz are in the largest sizes, the middle degree solid biotite and ferrous oxide are in the second degree. If extremely thin sized material is required, the surface of the quartz below 500 μ will be free and biotites will leave the surface. If 99% of mineral purity, high quality zeolite is required, it is concluded that the iron, hematite and biotites, which are present in trace amounts within the structure, can be removed by magnetic separation. In the broken grain material below the 1 × 1.5 mm zeolite sample size, ferrous oxide mineral daubing (yellowish, reddish) and partially free and mostly pointed clamped biotite grains are observed. This shows that the zeolite is contaminated. According to the request of the usage fields, this type of zeolite can be selectively disintegrated below 1 mm or 0.5 mm and can be subjected to density-dependent enrichment in order to obtain a cleaner product. It is observed and imaged that, the zeolite sample has more intense quartz and ferrous oxide and grains clamped with other biotite, compared to zeolite, and it is possible via a clean process, for example surface attraction to obtain cleaner crystal quartz. Crystal quartzes are in the sizes of 433 -373 μ and it is observed that if the zeolite sample is subjected to selective and protective disintegration under 400 μ and enriched according to dry or damp density, followed by a magnetic enrichment, clean crystal quartzes can be obtained. The obtained quartz can be used in the glass or ceramic sector. It is concluded that zeolite mineral is relatively clean, but for very high quality production, it should be downsized to below 150 μ and the contaminating minerals must go free and with a dry or damp environment enrichment, it is possible to obtain a multi quality zeolite concentrate. It has been proven with microscopic analysis and in digital media that clean zeolite grains mostly go free in a wide spectrum from 600 μ to 300 μ and even thinner. If it is milled down to these sizes and enriched in a dry and damp environment quality zeolite concentrate production will be possible. Within the scope of this study, according to the microscopic analyses results carried out towards the assessment of the structural features of Manisa Gordes zeolites, it should be considered that structural contaminant gang minerals must be removed and quality zeolite should be obtained with ore preparation and enrichment methods. Based on the ore formation, realisation of selective mining should be taken into consideration in zeolite production. Environmental contamination should be avoided and preventive production measures should be taken on this matter (for example: dust suppression curtains should be used.
Morphological analyses were carried out using SEM. SEM observations showed the presence of micro-particles in the shape of smooth surface. Displays of an electron microscopy of zeolite minerals are shown in Figure 4.

Conclusions
In Turkey, clinoptilolites are generally used in agriculture and stockbreeding.
The clinoptilolite group of zeolites with 85% purity has many areas of usage, according to their size. In this case, products gathered from primary crushing

O. Bilgin
can be used in gas purification. Products under 5 mm and gathered from secondary crushing can be used in water filtering (filtration) or put into use as animal mat or fertiliser additive. These processes generally use zeolites of 2 -5 mm.
The zeolites used in this study should be used for industrial areas and the improvement of agricultural lands. Zeolites that show efficiency in agricultural production and are needed to produce economic efficiency in water and fertiliser are carried out using consciously. Especially in Turkey, soil pollution created by immoderate use of water and fertiliser is eliminated by the use of zeolites.
They are used in the prevention of heavy metal pollution such as Pb, Cu, Zn, Cd and Hg, which pollute the environment via industrial wastes in solid, liquid, gas.
The use of zeolite via high adsorption force will contribute to preventing toxic contamination created by heavy traffic caused by heavy metal gases (Pb, Cu, Zn, Cd and Hg) nowadays and achieve a healthy environment for both people and cities. Therefore, Gördes zeolites should be considered for this purpose. The investigations indicate that it is also used as an additive for cement, which is more economical with lightweight structural elements in the construction industry, which can be done with zeolite. According to the results of microscopic examination in order to identify the structural features of Manisa Gordes zeolite, removing polluting gangue minerals in the structure and production of more quality zeolite provided by mineral processing and beneficiation methods should be considered. Based on the formation of ore, selective mining for production of zeolite should be considered. We should avoid environmental pollution and precautions should be taken for this required production (for instance, using a dust holding curtain).