How Zeolites are Formed?

Natural zeolite is a hydrated alumino silicate compound, with the main element consisting of alkaline cations and alkaline earth. These compounds have a three-dimensional structure and have pores that can be filled by water molecules.

The most common zeolite mineral is clinoptirotite, which has the chemical formula (Na3K3) (Al6Si30O72) .24H2O. The Na + and Ka + ions are interchangeable cations, while the Al and Si atoms are the cation and oxygen structures that will form the tetrahedron structure in zeolites. Molecules – Water molecules contained in zeolites are molecules that are easily separated.

Natural zeolite is formed from the reaction between fine-grained tuff acidic rocks with pore water or meteoric water. The use of Zeolite is for raw materials for water treatment, cleaning wastewater, household waste, agriculture industry, animal husbandry, fisheries, cosmetics, pharmaceutical industries and others.

Read: Natural Zeolite Exploration in Indonesia

Zeolites are formed from volcanic ash that settled millions of years ago. The properties of zeolite minerals vary greatly depending on the type and content of zeolite minerals. The zeolite mineral is found in pyroclastic sedimentary rocks. Natural zeolites are formed from the reaction between fine-grained tuffic acid tuffs which are rhyolitic with pore water or meteoric water (rainwater). The minerals included in the zeolite group are formed from the sedimentation of volcanic ash that has undergone an alteration process. Geologically, zeolite deposits are formed due to the process of sedimentation of volcanic dust in the lake environment that is alkaline (saltwater), diagenetic processes (low-level metamorphosis), and hydrothermal processes.

Zeolite is formed when especially rough volcanoes ejected gigantic measures of debris containing aluminosilicates of antacid and basic earth. A portion of the breeze borne debris settled to shape thick debris beds.

More often than not debris falls into the sea it just becomes silt or onto land and it just becomes soil. In some different cases the debris may fall into lakes. These lakes can’t be seawater or new water yet should be a semi-saline lake. In the event that the science of the lake is in the correct range the concoction response of volcanic debris and in not many salts in the water will bring about the arrangement of a characteristic zeolite. The material is supposed to be zeolitized.

Qualities of every zeolite store will differ because of the conditions of its arrangement. Normal contrasts, for example, temperature, geographic area, and the proportion and convergence of the different salts figure out which specific zeolite minerals are framed.

These distinctions during the arrangement of a zeolite store are the explanation that every common zeolite store has one of a kind property. Our zeolite is crystalline significance it is very hard contrasted with most normal zeolite stores. When we process it to a specific molecule size it will hold its size under run of the mill taking care of and from a wetting or drying process.

Traditional open-pit mining methods are utilized to mine characteristic zeolites. The overburden is expelled to permit access to the metal. The mineral might be impacted or stripped for preparing by utilizing tractors furnished with ripper cutting edges and front-end loaders. In preparing, the metal is squashed, dried, and processed. The processed mineral might be air-delegated to molecule size and sent in packs or mass. The squashed item might be screened to evacuate fine material when a granular item is required, and some pelletized items are delivered from fine material.

Starting in 2016 the world’s yearly creation of normal zeolite approximates 3 million tons. Significant makers of zeolite in 2010 including China (2 million tons), South Korea (210,000 tons), Japan (150,000 tons), Jordan (140,000 tons), Turkey (100,000 tons) Slovakia (85,000 tons) and the United States (59,000 tons).The prepared accessibility of zeolite-rich stone easily and the lack of contending minerals and rocks are presumably the most significant components for its huge scope use. As indicated by the United States Geological Survey, almost certainly, a huge level of the material sold as zeolites in certain nations is ground or sawn volcanic tuff that contains just a modest quantity of zeolites. A few instances of such utilization incorporate measurement stone (as a changed volcanic tuff), lightweight total, pozzolanic concrete, and soil conditioners.

Zeolite Potential for Processing Industrial and Radioactive Waste

industrial waste processing with zeolite

Zeolite natural minerals are usually still mixed with other minerals such as calcite, gypsum, feldspar, and quartz and are found in areas around the volcano or settling in hot spring areas. Zeolites are also found as sedimentary rocks in basalt type soils and their chemical composition depends on the hydrothermal conditions of the local environment, such as temperature, local vapor pressure, and groundwater composition of the location. That makes zeolites with the same color and texture may differ in their chemical composition when taken from different locations, due to the combination of minerals in the form of fine particles with other impurities.

Sizable zeolite natural mineral deposits are found in several countries such as the United States, the Soviet Union, Japan, Australia, Cuba, and some eastern European countries such as the Czech Republic and Hungary.

In Indonesia, zeolites were discovered in 1985 by PPTM Bandung in large numbers, including scattered in several regions of Sumatra and Java. However, of the 46 zeolite locations, only a few locations were intensively mined, including in Bayah, Banten, Cikalong, Tasikmalaya, Cikembar, Sukabumi, Nanggung, Bogor and Lampung.

The use of zeolites is still not widely known, which at present zeolites in Indonesia are marketed in the form of nature, especially in the fertilization of agriculture. The following will discuss the potential of zeolites in waste treatment.

In 1984 Professor Joseph V. Smith the United States crystallographer defined zeolite as:

“Zeolite is an aluminosilicate with a framework structure enclosing cavities occupied by large ions and water molecules, both of which have considerable freedom of movement, permitting ion-exchange and reversible dehydration”.

As such, zeolites are minerals consisting of hydrated aluminosilicate crystals containing alkaline or alkaline earth cations in a three-dimensional framework. The metal ions can be replaced by other cations without damaging the zeolite structure and can absorb water reversibly.

At present, there are about 40 species of natural zeolites, although there are about 12 types of commercial value, including clinoptilolite, mordenite, filipsite, kabasite, and erionite. Synthetic zeolites are produced from several companies such as Union Carbide, ICI and Mobil Oil, and more than 100 species have been recognized, including zeolite A, X, Y, ZSM / AlPO4 group (Zeolite Sieving Materials / Aluminum Phosphate) and even recently known Zeotip groups, namely materials such as zeolites but not alumino-silicate compounds.

Read : Natural Zeolite Exploration in Indonesia

In the zeolite structure, all Al atoms are in tetrahedral form so that Al atoms will be negatively charged because they coordinate with 4 oxygen atoms and are always neutralized by alkaline or alkaline earth cations to reach stable compounds. Another case with clay rocks (clay materials) with a structural layer, where the ion exchange properties are caused by 1) broken bonds, namely the smaller the absorption particles the larger, 2) hydroxide groups where hydrogen atoms can be replaced with other cations or 3) substitution isomorph Al in tetrahedral Si causes Al-Si bonds to be quite strong and reduce swelling.

The ability of ion exchange (sometimes with the term absorption ability of ions or sorption) zeolites is the main parameter in determining the quality of zeolites to be used, usually known as CEC (cation exchangeability). CEC is the number of metal ions that can be absorbed maximum by 1 g of zeolite under equilibrium conditions.

Zeolite granular
Zeolite granular

For the separation of ammonia/ammonium ions from industrial wastewater, for the separation of fission products from radioactive waste and use in the field of agricultural waste. Clinoptilolite can separate 99% of ammonia/ammonium from industrial waste. Tsitsisvii (1980) and Blanchard (1984) found clinoptilolite can also separate heavy metals (Pb, Cu, Cd, Zn, Co, Ni, and Hg) both in industrial waste or in agricultural soils for “soil conditioning”. In treating nuclear waste, Ames from 1959-1962 was a researcher using clinoptilolite for the separation of radioactive substances. Finally, clinoptilolite has also been used to decontaminate reactor cooling water in the Three Mile Island reactor accident in America in 1979 (10). Zeolite was also used to decontaminate the cooling water of the Three Mile Island Unit II reactor and in 1987 to absorb radioactive gas in the Chernobyl reactor which caught fire.

Zeolite from the California deposit is used for the separation of fission radionuclides in nuclear fuel storage pool water at the British Nuclear Fuel Limited’s SIXEP (Site Ion-Exchange Plant), Sellafield, UK. In addition to sand substitutes, a mixture of zeolites, fly ash, and slugs are used in the cement cementation process. In the United Kingdom and Korea, cementation waste does not use sand because the sand will increase the volume of waste contrary to the principle of “minimized waste” or volume reduction.

Natural Zeolite Exploration in Indonesia

Zeolites are a group of minerals which in the sense/naming of minerals are one type of non-metal minerals or industrial mineral minerals from 50 existing types. Until now more than 50 natural zeolite forming minerals have been known, but only nine of them are often found, namely clinoptilolite, mordenite, analsim, khabasit, erionite, ferrierite, heulandite, laumonite, and filipsite. From the results of investigations that have been done, the types of zeolite minerals found in Indonesia are modernite and clinoptilolite.

This natural zeolite is formed from a reaction between fine-grained acidic acid and rhyolitic tuffs with pore water or meteoric water (rainwater). This mineral is a group of hydrated aluminosilicates with the main elements consisting of cations, alkalis, and alkaline soils, having pores that can be filled by water molecules. The water content trapped in the zeolite cavity is usually around 10-50%. When hydrated cations in the cavity will be covered with water molecules, these water molecules are unstable or easily detached. The general nature of zeolites, among others, have a rather soft crystal structure, a specific gravity of 2-2.4, turquoise, white and brown.

Geologically, zeolites begin to be found in tuff rocks formed from the results of sedimentation, volcanic dust that has undergone an alteration process. There are four processes as a picture of starting to become zeolite, namely the process of volcanic dust sedimentation in an alkaline lake environment, alteration process, diagenesis process and hydrothermal process.

It has been mentioned that water molecules found in zeolites are unstable so that by heating above 100 degrees celsius, the pore water can be expelled so that zeolite pores are formed which can allow zeolites to absorb molecules that have smaller diameters than zeolite pores the.

In addition to natural zeolites, there are also types of artificial zeolites, each of which has advantages and disadvantages compared to each other. Artificial zeolite consists of aluminosilicate gel by imitating the hydrothermal process in one of the processes starting to become natural zeolite. This type of gel is made from a solution of sodium aluminate, sodium silicate, and sodium hydroxide. There are three types of chemicals on the market that are of the same use as natural zeolites, namely activated carbon, silica gel, and artificial zeolites.

Based on research, the ability of activated carbon and silica gel as an absorber did not exceed natural zeolites. Artificial zeolites can indeed be purer and have broader capabilities compared to natural zeolites, especially as catalysts. The use of zeolite has been developed in such a way that it can be used for several purposes in industry and agriculture, also for the environment, especially to eliminate odors, because zeolites can absorb gas molecules such as CO, CO2, H2S, and others. Zeolites are non-metallic minerals or multi-use industrial minerals because they have unique physical and chemical properties, namely as an absorber, ion exchange, molecular filter, and as a catalyst.

Exploration of the field done by surveying and mapping the spot at first. When compared with the other areas in the world, Indonesian zeolites are young in geological terms. From the Rotorua’Taupo, it can be recognized that intense volcanic activity have been occurred about 250.000 years ago. The deposits might be located in layers of sediment approximately 30 metres depth or even more.

For sampling, an excavator will dig pits in the survey area to get samples. The samples are then tested using x-ray diffraction. Zeolites use unique crystal structure with many unique surfaces. Zeolite minerals in Indonesia have properties which are slightly different than other countries Zeolite. By way of example. Zeolite powder like in the Taupo Volcanic Zone have soft and porous properties.

There are approximately 40 minerals known as zeolites. One minerals found in the Taupo Volcanic Zone is really a silica-rich mineral called Clinoptilolite. Mineral that is used in agriculture and also in the oil market.

Once big deposit confirmed commercial viability, a quarry is produced to extract the mineral. In Indonesia, there are many quarries where mineral ore is mined. Open-pit mining may be the type used in Zeolite Indonesia. Usually, overburden is first stripped to allow access to the ore. The ore is then drilled or stripped. and hydraulic excavators are then employed for loading. The raw material might be crushed and screened on mining site and positioned in stockpiles for drying from the outside. or it just transported towards the processing mill where it will likely be crushed and screened.

Natural and Synthetic Zeolite

Zeolites are hydrated aluminosilicate compounds consisting of SiO4 and AlO4 tetrahydra bonds connected by oxygen atoms to form a skeleton. In the zeolite framework, each Al atom is negative and will be neutralized by bonds with easily interchangeable cations. The easily interchangeable cations present in this zeolite framework influence the adsorption process and the thermal properties of zeolites. In addition to the type of cation, the zeolite adsorption ability is also influenced by the Si / Al ratio and the geometry of the zeolite pores, including of inner surface, pore-size distribution, and also pore shape. Zeolites occur naturally at the surface of the soil. At present many types of natural zeolites have been found and grouped according to their structural similarity.

Zeolite is one type of rock containing several alumino silica minerals that are hydrated from alkaline cations and alkaline soils which have a porous structural framework, are easy to boil and expand when heated (Anwar, 1987). Zeolites have a three-dimensional structure with cavities in which contain metal ions, the zeolite molecular formula, namely Mx / n [(AlO2) x (SiO2) y] mH2O where M is a validation cation n, (AlO2) x ( SiO2) y is a negatively charged zeolite framework, while x and y are total tetrahedral numbers per unit cell and the x / y ratio is always around 1 to 5, and H2O is the hydrated water molecule in the zeolite framework.

Zeolites are composed of elements of aluminum (Al), silicon (Si), oxygen (O2), and contain cations (+ ions) and water (Ballard, et al., 1988). The more complete chemical composition of zeolite consists of Silica (SiO2) 68.3%, Aluminum Oxide (Al2O3) 12.3%, Iron (Fe2O3) 0.1%, Calcium (Ca) 4.3%, Magnesium (Mg) 1, 1%, Sodium (Na2O) 0.3%, and Potassium (K2O) 1.0%.

Zeolites can be obtained through two types of sources, natural zeolites and zeolite synthesis. Natural zeolites are formed due to the complex chemical and physical processes of rocks undergoing various kinds of changes in nature. Geochemists and mineralogists has estimated that zeolites are volcanic products that freeze to volcanic rocks, sedimentary rocks and metamorphic rocks which subsequently undergo weathering due to the effects of heat and cold. As a natural product, natural zeolites are known to have very varied compositions, but the main components are silica and alumina. In addition to these main components, zeolites also contain various minor elements, including Na, K, Ca, Mg, and Fe.

Apart from its wide application, natural zeolite has several disadvantages, including containing many impurities such as Na, K, Ca, Mg and Fe as well as poor crystallinity. The presence of these impurities can reduce the activity of zeolites. To improve the character of natural zeolites so that they can be used as catalysts, adsorbents, or other applications, activation and modification are usually done first.

Synthetic zeolites are zeolites that are engineered in such a way as to obtain better character than natural zeolites. The basic principle of synthetic zeolite production is its component consisting of silica and alumina, so that it can be synthesized from various raw materials containing the two components above. Minor components in zeolites can also be added easily using pure compounds, so synthetic zeolites have a fixed composition with a high degree of purity.

the difference between natural zeolites and synthetic zeolites is:

1. Synthetic zeolites are made from chemicals and natural ingredients which are then processed from the natural seed body.

2. Synthetic zeolites have a ratio of silica and alumina which is 1: 1 and on natural zeolites up to 5: 1

3. Natural zeolites are not separated in an acidic environment like synthetic zeolites

 

Thank you for reading our article. Keep in touch with Nusagri to get more information about zeolite. Nusagri.co.id is the pioneer in exploitation and processing of zeolite minerals in Indonesia used in Agricultural and multi sectors. Nusagri exported tons of zeolite for many countries including India and Malaysia. Please check our website and social media for further information about zeolite.

Effect of Zeolite in Fertilizer

Natural zeolites are known for their benefit on many aspects. They are used in many things include cosmetic, automotive, and agriculture. In agriculture, natural zeolites have been used as feed additive, water conditioner, soil conditioner, and even for growing medium for hydroponics. Farmers used zeolite for good reason. It could help their plants have more nutrients or bind heavy metals that cause bad effect on fish, or reducing ammonia production from animal feces.

Benefit of natural zeolite in agriculture have been mentioned in our article before. Please check our article about Uses of Zeolite in Agriculture, and check our full articles at Nusagri’s Blog. In this article, we will discuss about zeolite application in fertilizer for plants. The discussion included properties of zeolite and how zeolite affect the growth of plants.

Natural Zeolite came along with volcano eruption. Geochemists and mineralogists estimate that zeolites are the product of frozen volcanoes into volcanic rocks, sedimentary rocks and metamorphic rocks which subsequently undergo weathering due to the influence of heat and cold so that zeolite minerals eventually formed.

Zeolite properties have been discovered by studies. As result, studies found that zeolite contained up to 70% of high ration between silica and aluminum oxides. Study also found morphology of the porous structure on natural zeolites that able to absorb and desorb substances. Zeolite also have ability to selective adsorption of large cations. This is due to the proximity of the ions size that defined as strong Coloumb interaction with structure of zeolite. Their physicochemical properties essentially depend on the content of the
zeolitic phase in the rock, such as cations exchange form and nature of impurities. Natural zeolites are porous systems, the primary porosity of them is determined by the micropores of crystals, and the secondary one – by the transitional pores and macropores. Natural zeolites start to be applied on multi sectors of agriculture. One of them is become fertilizer mixer for plants growth.

Plants can growth because of soil as their growing medium that contain water and nutrients as growing needs. Those are required for photosynthesis reaction to produce energy. Photosynthesis create food for plants using water, carbon dioxides, sun light, and minerals. That make plants grow and produce resource for us. Soil is one of the most important environmental factors and is considered the main source in providing essential plant nutrients, water reserves and a medium for plant growth. Giving soil a fertilizer purposed to increase nutrients needed by plants like nitrogen, potassium, kalium, magnesium, calcium, and many more. With eligible nutrient, plants will produce higher quality and quantity of fruits and any parts that consumed by human. Each minerals affect certain effect on plants growth. Fertilizer also used to neutralizing soil pH for better environment.

Fertilizer is divided into two categories, organic fertilizer and inorganic fertilizer. Organic fertilizer is fertilizer obtained from weathering and decomposition of organic materials that exist in nature, for example compost. Organic fertilizer is difficult to regulate its nutrient content so it is not necessarily suitable to the needs of plants. Meanwhile, inorganic fertilizers are fertilizers made with certain mineral contents so that they have the quantities needed by plants.

Studies found the effect of zeolite in fertilizer. The experiment showed that fertilizer mixed with zeolite resulted in the same growth and productivity, although the fertilizing doses were reduced. This means that zeolite increase fertilizing efficiency. This is because of zeolite properties. Zeolites have porous surface that able to bind nutrients.

Mostly, fertilizer will lose their nutrients by earth-water flow underground. These nutrients carried away by water, so it can’t be absorbed by plants. This case occurred often during rainy season. Rainy season decrease fertilizer efficiency in soil. Zeolite bind nutrients so they are not carried away by water. This is needed not only in rainy season, but also in any season. Fertilizer consumption is decrease with zeolite.

That’s all of our article today. The conclusion is zeolite will increase the efficiency of fertilizer. Zeolite will decrease the consumption of fertilizer for plants. Zeolite can adsorb substance because of is porous properties. Within fertilizer, zeolite bind nutrients  so they are not easily carried away by water in soil.

Thank you for reading our article. Keep in touch with Nusagri to get more information about zeolite. Nusagri.co.id is the pioneer in exploitation and processing of zeolite minerals in Indonesia used in Agricultural and multi sectors. Nusagri exported tons of zeolite for many countries including India and Malaysia. Please check our website and social media for further information about zeolite. 

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