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.

Improving the Quality of Biogas Fuels with Natural Zeolites

biogas

Human dependence on fossil fuels causes reserves of energy sources is increasingly diminishing, besides it also impacts on the environment, such as air pollution. Fossil fuels or mineral fuels are natural resources that contain hydrocarbons such as coal, petroleum, and natural gas. 

Fossil fuels are formed because of the natural process of decay from organisms that died hundreds of millions of years ago. Dinosaurs, trees, and almost all living things that died were deposited on the ground and now have become petroleum, natural gas, or coal. Natural gas has the form of gas, liquid petroleum, and solid coal. due to differences in the pressure and heat, they receive in the bowels of the earth over millions of years ago.

Fossil fuels are a kind of non-renewable natural resource. Because this fossil fuel is formed from the process of sedimentation and decomposition of living things and takes millions of years. 

This makes many people aware that dependence on fossil fuels must be reduced immediately. To overcome this problem, alternative fuels that are cheap and easy to obtain are needed. One of the alternative fuels is biogas. 

Biogas is a gas produced by anaerobic activity or fermentation of organic materials including human and animal feces, domestic (household) waste, biodegradable waste, or any biodegradable organic waste in anaerobic conditions. The main material in making biogas are Methane and Carbon Dioxide. Biogas also can be used as vehicle fuel or to turn on electric things.

Biogas is reprocessed into more specific fuel oil. The process of purification (purification) of natural gas or often also called the process of gas purification is carried out with the aim of removing/separating impurities (impurities) that are not desired in the natural gas. Before the purification process is carried out, natural gas obtained from the well must first go through a testing phase in the laboratory to find out the chemical compounds that are dissolved in it. This is needed to determine the purification process, the number of processing units, the type of chemical, and the chemical dose to be used. The addition of activated carbon in raw materials in the form of cow dung serves to increase the C / N ratio, which can improve the anaerobic digestion process and obtain optimum conditions in producing methane gas. The study also used a CO2 scrubber with a solution of Ca (OH) 2 (lime water) and KOH solution.

Biogas is produced through the process of fermentation of organic waste such as garbage, food scraps, animal waste and food industry waste. The elements contained in biogas are methane gas (CH4), carbon dioxide gas (CO2), oxygen gas (O2), hydrogen sulfide gas (H2S), hydrogen gas (H2), and carbon monoxide gas (CO).

Of all these elements that play a role in determining the quality of biogas, namely methane (CH4) and carbon dioxide (CO2) gas. If the CH4 level is high, the biogas will have a high heating value. Conversely, if CO2 levels are high, the biogas calorific value will be low. Therefore to increase the heating value of biogas the CO2 gas content must be low. The content of methane gas (CH4) from biogas can be increased by separating corrosive carbon dioxide (CO2) and hydrogen sulfide (H2S) gas from biogas.

To overcome this problem, many attempts were made to refine biogas. Researchers studied the biogas purification process using zeolite which was activated with a solution of NaOH and the zeolite was modified by mixing several materials such as bentonite, kaolin, limestone, tapioca/starch, and liquid chitosan. In addition, other efforts have also been made to improve the quality and quantity of biogas, namely the addition of activated carbon and the use of CO2 scrubbers.

Read: Zeolite Uses In Agriculture

An interesting method of biogas purification to be studied is by using adsorbents. The adsorbent is a substance that can absorb fluid, both liquid, and gas so that later it will form a thin layer on the surface of the substance. One type of adsorbent that can be used is zeolite.

Zeolite was chosen because besides being easily obtained, the price was also quite cheap. So that the zeolite adsorption process takes place faster than before the activation process should be done first. The activation process can be done in two ways, namely physically with the heat treatment process and chemically using an acid or base solution. One type of chemical that can be used for the chemical activation process is potassium hydroxide (KOH) or its Latin name, Potassium Hydroxide. KOH is a strong base compound that is stable and dissolves easily.

Benefits of Zeolite for Shrimp Pond

Zeolit benefit for shrimp pond

Shrimp ponds are businesses in the fishery sector that involve ponds containing freshwater, saltwater, and brackish water. Shrimp is one type of filter animal so that water quality is crucial for the results obtained by farmers. Potential shrimps to be cultivated in ponds are tiger shrimp (Penaeus monodon) and vaname shrimp (Litopenaeus vannamei). Both are able to tolerate salt levels between 0 to 45 percent.

 

Zeolites are natural minerals made from aluminum silicate groups that are hydrated by alkali metals and alkaline earth. The zeolite mineral is gray to bluish. Clinoptilolite is a type of natural zeolite mineral that has many uses.

 

In aquaculture, Clinoptilolite can be used to help control the quality of the soil at the bottom of a pond. Clinoptilolite forms like crystal and has a variety of colors, namely white, yellow, pink, and pale brown.

 

In this article, Nusagri discusses the benefits of zeolite for shrimp ponds. Nusagri has also published related articles,  Zeolite as ammonia adsorber in pond. Please refer to the article.

Pond water quality is an important thing that must always be considered. According to research, if environmental conditions such as water quality are not in accordance with the standards for cultivation it will cause death and ultimately losses in aquaculture. Water quality management is a way to maintain water quality parameters in accordance with quality standards for cultivation. These parameters are an indicator to see the quality of water, such as dissolved oxygen (DO), free carbon dioxide (CO2), pH, temperature, brightness, salinity, ammonia, and nitrite.

Zeolit benefit for shrimp pond

Dissolved oxygen should be sufficient. Scientists generally agree that aquatic animals need dissolved oxygen at a concentration of 5.0 mg / L or more to be able to live and develop. However, the amount of oxygen needed can also vary depending on how large or complex the animal is and where it lives. The greater the dissolved oxygen value, the better the water quality. The highest difference in dissolved oxygen concentration is found in waters that have high plankton density and vice versa. Most of the waters that have low oxygen levels are caused by a variety of complex factors from natural to man-made factors. The solubility of oxygen in water is influenced by several factors including temperature, salinity of the waters, movement of water on the surface of the water, the surface area of open waters, atmospheric pressure, and the percentage of oxygen around it.

 

When the concentration of dissolved oxygen is low, carbon dioxide levels can inhibit the entry of oxygen into pond water. The normal range of carbon dioxide is from 1 to 10 mg / l. If carbon dioxide exceeds 10 mg / l, the water quality is not good.

 

Too high pH is not good, a pH above 8.5 causes ammonia in the pond to be toxic and raises hydrogen sulfide around it which is also a toxic substance, so don’t overdo it.

 

Temperature or temperature is one indicator of the success of shrimp farming. For this reason, temperature fluctuations must always be watched out for by farmers, because sudden spikes or decreases in temperature can inhibit shrimp growth and can even make shrimp die.

It should be noted by farmers that the optimal temperature for shrimp to grow and develop is in the range of 26 to 30 degrees celsius. As for the drastic temperature change that can be overcome by shrimp is no more than 2 degrees celsius. If the pond temperature decreases until it reaches 25 degrees Celsius, it can cause the digestibility of food by shrimp will be hampered, this will later influence the growth of shrimp. Vice versa, if there is a surge in temperature to reach 30 degrees Celsius or more, it will trigger stress on shrimp. The stress experienced is due to high-temperature changes that cause shrimp oxygen demand to increase.

 

To avoid stress on shrimp, pond entrepreneurs are required to always check the level of water salinity routinely. In general, the ideal shrimp ponds are shrimp ponds that have a salinity level of around 10-30 ppt.

 

Zeolite is useful for conditioning pond water quality to conform to shrimp pond standards. Various benefits of zeolite minerals for ponds, namely:

 

• Because it has a high absorption power, zeolite minerals can reduce gases in the remaining shrimp feed (not eaten), as well as gases originating from the metabolism of other organisms that live at the pond bottom.

• Zeolite minerals are able to bind heavy metals in water or pond bottom soils that can threaten the survival of fish/shrimp, such as Pb, Fe, Hg, Sn, Bi, and AS.

• Because zeolites have a high calcium content, shrimp in ponds can be prevented from soft skin diseases.

• Maintaining the stability of the water temperature, as well as maintaining the degree of acidity (pH) of water in a pond.

• Increase the level of dissolved oxygen in the water

• Helps the growth of phytoplankton in ponds, so that natural food for shrimp is always maintained.

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