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Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents and catalysts. ζέω (zéō), meaning "to boil" and λίθος (líthos), meaning "stone". The classic reference for the field has been Breck's book Zeolite Molecular Sieves: Structure, Chemistry, And Use.The term zeolite was originally coined in 1756 by Swedish mineralogist Axel Fredrik Cronstedt, who observed that rapidly heating the material, believed to have been stilbite, 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
A microporous material is a material containing pores with diameters less than 2 nm. Examples of microporous materials include zeolites and metal-organic frameworks.
Aluminosilicate minerals are minerals composed of aluminium, silicon, and oxygen, plus countercations. They are a major component of kaolin and other clay minerals.
A mineral is, broadly speaking, a solid chemical compound that occurs naturally in pure form. A rock may consist of a single mineral, or may be an aggregate of two or more different minerals, spacially segregated into distinct phases. Compounds that occur only in living beings are usually excluded, but some minerals are often biogenic and/or are organic compounds in the sense of chemistry. Moreover, living beings often synthesize inorganic minerals that also occur in rocks.
Zeolites occur naturally but are also produced industrially on a large scale. As of December 2018 [update] , 245 unique zeolite frameworks have been identified, and over 40 naturally occurring zeolite frameworks are known. Every new zeolite structure that is obtained is examined by the International Zeolite Association Structure Commission and receives a three letter designation.
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 of the mineral formula of a zeolite is: Na
10·2H2O, the formula for natrolite. These cation exchanged zeolites possess different acidity and catalyse several acid catalysis.
Analcime or analcite (from the Greek analkimos - "weak") is a white, gray, or colorless tectosilicate mineral. Analcime consists of hydrated sodium aluminium silicate in cubic crystalline form. Its chemical formula is NaAlSi2O6·H2O. Minor amounts of potassium and calcium substitute for sodium. A silver-bearing synthetic variety also exists (Ag-analcite).
Chabazite is a tectosilicate mineral of the zeolite group, closely related to gmelinite, with formula (Ca,Na2,K2,Mg)Al2Si4O12·6H2O. Recognized varieties include Chabazite-Ca, Chabazite-K, Chabazite-Na, and Chabazite-Sr, depending on the prominence of the indicated cation.
Clinoptilolite is a natural zeolite comprising a microporous arrangement of silica and alumina tetrahedra. It has the complex formula: (Na,K,Ca)2-3Al3(Al,Si)2Si13O36·12H2O. It forms as white to reddish tabular monoclinic tectosilicate crystals with a Mohs hardness of 3.5 to 4 and a specific gravity of 2.1 to 2.2. It commonly occurs as a devitrification product of volcanic glass shards in tuff and as vesicle fillings in basalts, andesites and rhyolites. It was described in 1969 from an occurrence in Owl Canyon, San Bernardino County, California.
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.
Volcanic ash consists of fragments of pulverized rock, minerals and volcanic glass, created during volcanic eruptions and measuring less than 2 mm (0.079 inches) in diameter. The term volcanic ash is also often loosely used to refer to all explosive eruption products, including particles larger than 2 mm. Volcanic ash is formed during explosive volcanic eruptions when dissolved gases in magma expand and escape violently into the atmosphere. The force of the escaping gas shatters the magma and propels it into the atmosphere where it solidifies into fragments of volcanic rock and glass. Ash is also produced when magma comes into contact with water during phreatomagmatic eruptions, causing the water to explosively flash to steam leading to shattering of magma. Once in the air, ash is transported by wind up to thousands of kilometers away.
Quartz is a mineral composed of silicon and oxygen atoms in a continuous framework of SiO4 silicon–oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical formula of SiO2. Quartz is the second most abundant mineral in Earth's continental crust, behind feldspar.
Zeolites are the aluminosilicate(AlO4 5- and SiO4 4-) members of the family of microporous solids known as "molecular sieves", and mainly consist of Si, Al, O, and metals including Ti, Sn, Zn, and so on. 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 eight tetrahedrally coordinated silicon (or aluminium) atoms and 8 oxygen atoms. These rings are not always perfectly symmetrical due to a variety of causes, 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.
A molecular sieve is a material with pores of uniform size. These pore diameters are similar in size to small molecules, and thus large molecules cannot enter or be adsorbed, while smaller molecules can. As a mixture of molecules migrate through the stationary bed of porous, semi-solid substance referred to as a sieve, the components of highest molecular weight leave the bed first, followed by successively smaller molecules. Some molecular sieves are used in chromatography, a separation technique that sorts molecules based on their size. Other molecular sieves are used as desiccants.
Zeolites transform to other minerals under weathering, hydrothermal alteration or metamorphic conditions. Some examples:
Weathering is the breaking down of rocks, soil, and minerals as well as wood and artificial materials through contact with the Earth's atmosphere, water, and biological organisms. Weathering occurs in situ, that is, in the same place, with little or no movement, and thus should not be confused with erosion, which involves the movement of rocks and minerals by agents such as water, ice, snow, wind, waves and gravity and then being transported and deposited in other locations.
Metamorphism is the change of minerals or geologic texture in pre-existing rocks (protoliths), without the protolith melting into liquid magma. The change occurs primarily due to heat, pressure, and the introduction of chemically active fluids. The chemical components and crystal structures of the minerals making up the rock may change even though the rock remains a solid. Changes at or just beneath Earth's surface due to weathering or diagenesis are not classified as metamorphism. Metamorphism typically occurs between diagenesis, and melting (~850°C).
Industrially important zeolites are produced synthetically. Typical procedures entail heating aqueous solutions of alumina and silica with sodium hydroxide. Equivalent reagents include sodium aluminate and sodium silicate. Further variations include changes in the cations to include quaternary ammonium cations.
Synthetic zeolites hold some key advantages over their natural analogues. The synthetic materials are manufactured in a uniform, phase-pure state. It is also possible to produce zeolite structures that 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.
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.
As of 2016 [update] the world's annual production of natural zeolite approximates 3 million tonnes. Major producers in 2010 included 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 the United States (59,000 t). 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 include dimension stone (as an altered volcanic tuff), lightweight aggregate, pozzolanic cement, and soil conditioners.
There are over 200 synthetic zeolites that have been synthesized by a process of slow crystallization of a silica-alumina gel in the presence of alkalis and organic templates. Many more such structures could theoretically be made.In addition to variations in structures, zeolites can also be made with a variety of other atoms in them to make them chemically interesting and active. Some examples of the so-called heteroatoms that have been incorporated include germanium, iron, gallium, boron, zinc, tin, and titanium. 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. The ease of scaling up this process makes it a favorite route for zeolite synthesis.
Computer calculations have predicted that millions of hypothetical zeolite structures are possible. However, only 232 of these structures have been discovered and synthesized so far, so many zeolite scientists question why only this small fraction of possibilities are being observed. This problem is often referred to as "the bottleneck problem". Currently there are a number of theories attempting to explain the reasoning behind this question.
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 are also widely used as catalysts and sorbents. Their well-defined pore structure and adjustable acidity make them highly active in a large variety of reactions.
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.
Zeolites assist silver in naturally emitting light, which could lead to new lighting technologies—supplementing or replacing fluorescent lights or LEDs.
On-board oxygen generating systems (OBOGS) and Oxygen concentrators use zeolites in conjunction with pressure swing adsorption to remove nitrogen from compressed air in order to supply oxygen for aircrews at high altitudes, as well as home and portable oxygen supplies.
Synthetic zeolites, as other mesoporous materials (e.g. MCM-41), 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 acidic forms of zeolites prepared are often powerful solid-state solid acids, facilitating a host of acid-catalyzed reactions, such as isomerisation, alkylation, and cracking.
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 complete its cycle.
Zeolites have uses in advanced nuclear-waste reprocessing methods, where their micro-porous ability to capture some ions while allowing others to pass freely allows many fission products to be efficiently removed from the 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.
The German group Fraunhofer e.V. announced that they had developed a zeolite substance for use in the biogas industry for long-term storage of energy at a density 4x more than water.Ultimately, the goal is to be able to store heat both in industrial installations and in small combined heat and power plants such as those used in larger residential buildings.
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 (energy releasing) reaction when transitioning from a dehydrated to a hydrated form make natural zeolites useful in harvesting waste heat and solar heat energy. Zeolites are also used as a molecular sieve in cryosorption style vacuum pumps.
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 ]
Non-clumping cat litter is often made of zeolite or diatomite.
Synthetic zeolites are used as an additive in the production process of warm mix asphalt concrete. The development of this application started in Germany in the 1990s. They help 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. The use of synthetic zeolites 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 they can reduce chloride permeability and improve workability. They reduce weight and help moderate water content while allowing for slower drying which improves break strength.When added to lime mortars and lime-metakaolin mortars, synthetic zeolite pellets can act simultaneously as pozzolanic material and water reservoir.
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. 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, purple, 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 a "cat's eye" effect (chatoyancy).
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.
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,contains a calcium-loaded form of zeolite found in kaolin clay.
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 absorb up to 55% of their weight in water and slowly release it under the plant's demand. This property can prevent root rot and moderate drought cycles. Clinoptilolite has also been added to chicken food: the absorption of water and ammonia by the zeolite made the birds' droppings drier, less odoriferous and hence easier to handle.
Pet stores market zeolites for use as filter additives in aquaria,where they can be used to adsorb ammonia and other nitrogenous compounds. They must be used with some care, especially with delicate tropical corals that are sensitive to water chemistry and temperature. 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 also 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 aquarium applications. 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. The mechanism is well known to chemists as ion exchange. These sodium ions will speciate[ clarification needed ] with other ions in solution, thus the takeup of nitrogen in ammonia, with the release of the sodium. A deposit near Bear River in southern Idaho, (US) is a fresh water variety (Na < 0.05%). Southern hemisphere zeolites are typically formed in freshwater and have a high calcium content.[ citation needed ]
The zeolite structural group (Nickel-Strunz classification) includes:
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid is dissolved by or permeates a liquid or solid, respectively. Adsorption is a surface phenomenon, while absorption involves the whole volume of the material. The term sorption encompasses both processes, while desorption is the reverse of it.
Silica gel is an amorphous and porous form of silicon dioxide (silica), consisting of an irregular tridimensional framework of alternating silicon and oxygen atoms with nanometer-scale voids and pores. The voids may contain water or some other liquids, or may be filled by gas or vacuum. In the latter case, the material is properly called silica xerogel.
Stilbite is the name of a series of tectosilicate minerals of the zeolite group. Prior to 1997, stilbite was recognized as a mineral species, but a reclassification in 1997 by the International Mineralogical Association changed it to a series name, with the mineral species being named:
The ferrierite group of zeolite minerals (the FER structure) consists of three very similar species: ferrierite-Mg, ferrierite-Na, and ferrierite-K, based on the dominant cation in the A location. ferrierite-Mg and ferrierite-K are orthorhombic minerals and ferrierite-Na is monoclinic with highly variable cationic composition, (Na,K)2Mg(Si,Al)18O36(OH)·9H2O. Calcium and other ions are often also present. They are found in vitreous to pearly, often radiating, spherical aggregates of thin blade-shaped transparent to translucent crystals.
Heulandite is the name of a series of tecto-silicate minerals of the zeolite group. Prior to 1997, heulandite was recognized as a mineral species, but a reclassification in 1997 by the International Mineralogical Association changed it to a series name, with the mineral species being named:
A mesoporous material is a material containing pores with diameters between 2 and 50 nm, according to IUPAC nomenclature. For comparison, IUPAC defines microporous material as a material having pores smaller than 2 nm in diameter and macroporous material as a material having pores larger than 50 nm in diameter.
Mordenite is a zeolite mineral with the chemical formula, (Ca, Na2, K2)Al2Si10O24·7H2O. According to Ullmann's Encyclopedia of Industrial Chemistry (2005), it is one of the six most abundant zeolites and is used commercially.
Gmelinite-Na is one of the rarer zeolites but the most common member of the gmelinite series, gmelinite-Ca, gmelinite-K and gmelinite-Na. It is closely related to the very similar mineral chabazite. Gmelinite was named as a single species in 1825 after Christian Gottlob Gmelin (1792–1860) professor of chemistry and mineralogist from Tübingen, Germany, and in 1997 it was raised to the status of a series.
Gmelinite-Na has been synthesised from Na-bearing aluminosilicate gels. The naturally occurring mineral forms striking crystals, shallow, six sided double pyramids, which can be colorless, white, pale yellow, greenish, orange, pink, and red. They have been compared to an angular flying saucer.
Aluminium phosphate is a chemical compound. In nature it occurs as the mineral berlinite. Many synthetic forms of aluminium phosphate are known. They have framework structures similar to zeolites and some are used as catalysts, ion-exchangers or molecular sieves. Commercial aluminium phosphate gel is available.
Metal–organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. They are a subclass of coordination polymers, with the special feature that they are often porous. The organic ligands included are sometimes referred to as "struts", one example being 1,4-benzenedicarboxylic acid (BDC).
Zeolitic imidazolate frameworks (ZIFs) are a class of metal-organic frameworks that are topologically isomorphic with zeolites. ZIFs are composed of tetrahedrally-coordinated transition metal ions connected by imidazolate linkers. Since the metal-imidazole-metal angle is similar to the 145° Si-O-Si angle in zeolites, ZIFs have zeolite-like topologies. As of 2010, 105 ZIF topologies have been reported in the literature. Due to their robust porosity, resistance to thermal changes, and chemical stability, ZIF’s are being investigated for applications such as carbon capture.
ZSM-5, Zeolite Socony Mobil–5 (framework type MFI from ZSM-5 (five)), is an aluminosilicate zeolite belonging to the pentasil family of zeolites. Its chemical formula is NanAlnSi96–nO192·16H2O (0<n<27). Patented by Mobil Oil Company in 1975, it is widely used in the petroleum industry as a heterogeneous catalyst for hydrocarbon isomerization reactions.
SSZ-13 (framework type code CHA) is an aluminosilicate zeolite mineral possessing 0.38 × 0.38 nm micropores. It belongs to the ABC-6 family of zeolites as well as offretite, cancrinite, erionite and other related minerals. The framework topology is the same as that of chabazite but SSZ-13 has high-silica composition with Si/Al > 5 which leads to low cation exchange capacity. The typical chemical formula of the unit cell can be described as QxNayAl2.4Si33.6O72•zH2O (1.4 < x <27)(0.7 < y < 4.3)(1 < z <7), where Q is N,N,N-1-trimethyladamantammonium. The material was patented by Chevron research Company in 1985, and has a potential use as a solid catalyst for the methanol-to-olefins (MTO) process and the selective catalytic reduction (SCR) of NOx.
Faujasite is a mineral group in the zeolite family of silicate minerals. The group consists of faujasite-Na, faujasite-Mg and faujasite-Ca. They all share the same basic formula: (Na2,Ca,Mg)3.5[Al7Si17O48]·32(H2O) by varying the amounts of sodium, magnesium and calcium. It occurs as a rare mineral in several locations worldwide and is also synthesized industrially.
Gonnardite is a comparatively rare, fibrous zeolite, natrolite subgroup. Older papers claim that a complete solid solution exists between tetranatrolite and gonnardite, but tetranatrolite was discredited as a separate species in 1999. A series, based on the disorder of the silicon-aluminum in the framework, appears to exist between Na-rich gonnardite and natrolite, Na2(Si3Al2)O10·2H2O.
Mesoporous organosilica are a type of silica containing organic groups that give rise to mesoporosity. They exhibit pore size ranging from 2 nm - 50 nm, depending on the organic substituents. In contrast, zeolites exhibit pore sizes less than a nanometer. PMOs have potential applications as catalysts, adsorbents, trapping agents, drug delivery agents, stationary phases in chromatography and chemical sensors.
The purpose of a mineralizer is to facilitate the transport of insoluble “nutrient” to a seed crystal by means of a reversible chemical reaction. Over time, the seed crystal accumulates the material that was once in the nutrient and grows. Mineralizers are additives that aid the solubilization of the nutrient solid. When used in small quantities, mineralizers function as catalysts. Typically, a more stable solid is crystallized from a solution that consists of a less stable solid and a solvent. The process is done by dissolution-precipitation or crystallization process.
MCM-41 is a mesoporous material with a hierarchical structure from a family of silicate and alumosilicate solids that were first developed by researchers at Mobil Oil Corporation and that can be used as catalysts or catalyst supports.
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