Zeolite



Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents.[1] The term zeolite was originally coined in 1756 by Swedish mineralogist Axel Fredrik Cronstedt, who observed that upon rapidly heating the material stilbite, it produced large amounts of steam from water that had been adsorbed by the material. Based on this, he called the material zeolite, from the Greek ζέω (zéo̱), meaning "to boil" and λίθος (líthos), meaning "stone".[2] As of November 2010, 194 unique zeolite frameworks have been identified, and over 40 naturally occurring zeolite frameworks are known.[3][4] Zeolites are widely used in industry for water purification, as catalysts, for the preparation of advanced materials and in nuclear reprocessing. Their biggest use is in the production of laundry detergents. They are also used in medicine and in agriculture. Contents [hide] 1 Properties 2 Sources 3 Uses 3.1 Commercial and domestic 3.2 Petrochemical industry 3.3 Nuclear industry 3.4 Heating and refrigeration 3.5 Detergents 3.6 Construction 3.7 Gemstones 3.8 Vacuum pumping 3.9 Medical 3.9.1 Use as nutritional supplements 3.10 Agriculture 3.10.1 Animal husbandry 3.11 Domestic pet care 3.11.1 Aquarium keeping 3.11.2 Cat litter 4 Zeolite mineral species 5 See also 6 References 7 Further reading 8 External links [edit]Properties

A form of thomsonite (one of the rarest zeolites) from India Zeolites have a porous structure that can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+ and others. These positive ions are rather loosely held and can readily be exchanged for others in a contact solution. Some of the more common mineral zeolites are analcime, chabazite, clinoptilolite, heulandite, natrolite, phillipsite, and stilbite. An example mineral formula is: Na2Al2Si3O10·2H2O, the formula for natrolite. Natural zeolites form where volcanic rocks and ash layers react with alkaline groundwater. Zeolites also crystallize in post-depositional environments over periods ranging from thousands to millions of years in shallow marine basins. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, metals, quartz, or other zeolites. For this reason, naturally occurring zeolites are excluded from many important commercial applications where uniformity and purity are essential. Zeolites are the aluminosilicate members of the family of microporous solids known as "molecular sieves." The term molecular sieve refers to a particular property of these materials, i.e., the ability to selectively sort molecules based primarily on a size exclusion process. This is due to a very regular pore structure of molecular dimensions. The maximum size of the molecular or ionic species that can enter the pores of a zeolite is controlled by the dimensions of the channels. These are conventionally defined by the ring size of the aperture, where, for example, the term "8-ring" refers to a closed loop that is built from 8 tetrahedrally coordinated silicon (or aluminum) atoms and 8 oxygen atoms. These rings are not always perfectly symmetrical due to a variety of effects, including strain induced by the bonding between units that are needed to produce the overall structure, or coordination of some of the oxygen atoms of the rings to cations within the structure. Therefore, the pores in many zeolites are not cylindrical. [edit]Sources

Natrolith from Poland Conventional open pit mining techniques are used to mine natural zeolites. The overburden is removed to allow access to the ore. The ore may be blasted or stripped for processing by using tractors equipped with ripper blades and front-end loaders. In processing, the ore is crushed, dried, and milled. The milled ore may be air-classified as to particle size and shipped in bags or bulk. The crushed product may be screened to remove fine material when a granular product is required, and some pelletized products are produced from fine material. Currently, the world’s annual production of natural zeolite is about 3 million tonnes. The major producers in 2010 were China (2 million tonnes), South Korea (210,000 t), Japan (150,000 t), Jordan (140,000 t), Turkey (100,000 t) Slovakia (85,000 t) and United States (59,000 t).[5] The ready availability of zeolite-rich rock at low cost and the shortage of competing minerals and rocks are probably the most important factors for its large-scale use. According to the United States Geological Survey, it is likely that a significant percentage of the material sold as zeolites in some countries is ground or sawn volcanic tuff that contains only a small amount of zeolites. Some examples of such usage are dimension stone (as an altered volcanic tuff), lightweight aggregate, pozzolanic cement, and soil conditioners.[6]

Synthetic zeolite There are several types of synthetic zeolites that form by a process of slow crystallization of a silica-alumina gel in the presence of alkalis and organic templates. One of the important processes used to carry out zeolite synthesis is sol-gel processing. The product properties depend on reaction mixture composition, pH of the system, operating temperature, pre-reaction 'seeding' time, reaction time as well as the templates used. In sol-gel process, other elements (metals, metal oxides) can be easily incorporated. The silicalite sol formed by the hydrothermal method is very stable. Also the ease of scaling up this process makes it a favorite route for zeolite synthesis. Synthetic zeolites hold some key advantages over their natural analogs. The synthetics can, of course, be manufactured in a uniform, phase-pure state. It is also possible to manufacture desirable zeolite structures which do not appear in nature. Zeolite A is a well-known example. Since the principal raw materials used to manufacture zeolites are silica and alumina, which are among the most abundant mineral components on earth, the potential to supply zeolites is virtually unlimited. Finally, zeolite manufacturing processes engineered by man require significantly less time than the 50 to 50,000 years prescribed by nature. Disadvantages include the inability to create crystals with dimensions of a comparable size to their natural counterparts. [edit]Uses

[edit]Commercial and domestic Zeolites are widely used as ion-exchange beds in domestic and commercial water purification, softening, and other applications. In chemistry, zeolites are used to separate molecules (only molecules of certain sizes and shapes can pass through), and as traps for molecules so they can be analyzed. Zeolites have the potential of providing precise and specific separation of gases including the removal of H2O, CO2 and SO2 from low-grade natural gas streams. Other separations include noble gases, N2, O2, freon and formaldehyde. However, at present, the true potential to improve the handling of such gases in this manner remains unknown. On-Board Oxygen Generating Systems (OBOGS) use zeolites to remove nitrogen from compressed air in order to supply oxygen for aircrews at high altitudes.[7] [edit]Petrochemical industry Synthetic zeolites are widely used as catalysts in the petrochemical industry, for instance in fluid catalytic cracking and hydrocracking. Zeolites confine molecules in small spaces, which causes changes in their structure and reactivity. The hydrogen form of zeolites (prepared by ion-exchange) are powerful solid-state acids, and can facilitate a host of acid-catalyzed reactions, such as isomerisation, alkylation, and cracking. The specific activation modality of most zeolitic catalysts used in petrochemical applications involves quantum-chemical Lewis acid site reactions. Catalytic cracking uses reactor and a regenerator. Feed is injected onto hot, fluidized catalyst where large gasoil molecules are broken into smaller gasoline molecules and olefins. The vapor-phase products are separated from the catalyst and distilled into various products. The catalyst is circulated to a regenerator where air is used to burn coke off the surface of the catalyst that was formed as a byproduct in the cracking process. The hot regenerated catalyst is then circulated back to the reactor to. [edit]Nuclear industry Zeolites have uses in advanced reprocessing methods, where their micro-porous ability to capture some ions while allowing others to pass freely allow many fission products to be efficiently removed from nuclear waste and permanently trapped. Equally important are the mineral properties of zeolites. Their alumino-silicate construction is extremely durable and resistant to radiation even in porous form. Additionally, once they are loaded with trapped fission products, the zeolite-waste combination can be hot pressed into an extremely durable ceramic form, closing the pores and trapping the waste in a solid stone block. This is a waste form factor that greatly reduces its hazard compared to conventional reprocessing systems. Zeolites are also used in the management of leaks of radioactive materials. For example, in the aftermath of the Fukushima Daiichi nuclear disaster, sandbags of zeolite were dropped into the seawater near the power plant to adsorb radioactive caesium which was present in high levels.[8] [edit]Heating and refrigeration Zeolites can be used as solar thermal collectors and for adsorption refrigeration. In these applications, their high heat of adsorption and ability to hydrate and dehydrate while maintaining structural stability is exploited. This hygroscopic property coupled with an inherent exothermic (heat-producing) reaction when transitioning from a dehydrated to a hydrated form make natural zeolites useful in harvesting waste heat and solar heat energy. [edit]Detergents The largest single use for zeolite is the global laundry detergent market. This amounted to 1.44 million metric tons per year of anhydrous zeolite A in 1992.[citation needed] [edit]Construction Synthetic zeolite is also being used as an additive in the production process of warm mix asphalt concrete. The development of this application started in Germany in the 1990s. It helps by decreasing the temperature level during manufacture and laying of asphalt concrete, resulting in lower consumption of fossil fuels, thus releasing less carbon dioxide, aerosols, and vapours. Other than that, the use of synthetic zeolite in hot mixed asphalt leads to easier compaction and, to a certain degree, allows cold weather paving and longer hauls. When added to Portland cement as a pozzolan, it can reduce chloride permeability and improve workability. It reduces weight and helps moderate water content while allowing for slower drying which improves break strength.[9] [edit]Gemstones

Pollucite – rough and facetted.

Polished thomsonite Thomsonites, one of the rarer zeolite minerals, have been collected as gemstones from a series of lava flows along Lake Superior in Minnesota and to a lesser degree in Michigan, U.S.A. Thomsonite nodules from these areas have eroded from basalt lava flows and are collected on beaches and by scuba divers in Lake Superior. These thomsonite nodules have concentric rings in combinations of colors: black, white, orange, pink, red, and many shades of green. Some nodules have copper inclusions and rarely will be found with copper "eyes." When polished by a lapidary the thomsonites sometimes display chatoyancy.[10] [edit]Vacuum pumping Zeolites can be used as a molecular sieve in cryosorption style vacuum pumps.[citation needed] [edit]Medical Research into and development of the many biochemical and biomedical applications of zeolites, particularly the naturally occurring species heulandite, clinoptilolite and chabazite has been ongoing.[11] Zeolite-based oxygen concentrator systems are widely used to produce medical-grade oxygen. The zeolite is used as a molecular sieve to create purified oxygen from air using its ability to trap impurities, in a process involving the adsorption of nitrogen, leaving highly purified oxygen and up to 5% argon. QuikClot brand hemostatic agent, which is used to stop severe bleeding,[12] contains a calcium-loaded form of zeolite. [edit]Use as nutritional supplements Some clinoptilolite-based dietary supplements may have demonstrated antioxidant activity in humans. This has not been confirmed or repeated by any other group. There is no scientific or medical support for its use in immunotherapy.[13] [edit]Agriculture In agriculture, clinoptilolite (a naturally occurring zeolite) is used as a soil treatment. It provides a source of slowly released potassium. If previously loaded with ammonium, the zeolite can serve a similar function in the slow release of nitrogen. Zeolites can also act as water moderators, in which they will adsorb up to 55% of their weight in water and slowly release it under plant demand. This property can prevent root rot and moderate drought cycles. [edit]Animal husbandry "Both natural and synthetic zeolites have been used in animal nutrition mainly to improve performance traits and, based on their fundamental physicochemical properties, they were also tested and found to be efficacious in the prevention of ammonia and heavy metal toxicities, poisonings as well as radioactive elements uptake and metabolic skeletal defects."[14] In concentrated animal growing facilities, the addition of as little as 1% of a very low sodium clinoptiloite was shown to improve feed conversion, reduce airborne ammonia up to 80%, act as a mycotoxin binder, and improve bone density.[15] It can be used in general odor elimination for all animal odors.[6] [edit]Domestic pet care [edit]Aquarium keeping Zeolites are marketed by pet stores for use as a filter additive in aquariums.[6] In aquariums, zeolites can be used to adsorb ammonia and other nitrogenous compounds. However, due to the high affinity of some zeolites for calcium, they may be less effective in hard water and may deplete calcium. Zeolite filtration is used in some marine aquaria to keep nutrient concentrations low for the benefit of corals adapted to nutrient-depleted waters. Where and how the zeolite was formed is an important consideration for aquariums. Most Northern hemisphere natural zeolites were formed when molten lava came in contact with sea water, thereby 'loading' the zeolite with Na (sodium) sacrificial ions. These sodium ions will speciate with other ions in solution, thus the takeup of nitrogen in ammonia, with the release of the sodium. One deposit in southern Idaho near Bear River is a fresh water variety ( Na<.05%) In southern hemisphere zeolites, such as found in Australia, which were formed with fresh water, thus the calcium uptake on formation. Zeolite is an effective ammonia filter, but must be used with some care, especially with delicate tropical corals that are sensitive to water chemistry and temperature. [edit]Cat litter Non-clumping cat litter is often made of zeolite or diatomite.