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Wikipedia

Zeolite

Zeolite is a family of several microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts.[1] They mainly consist of silicon, aluminium, oxygen, and have the general formula Mn+
1/n
(AlO
2
)
(SiO
2
)
x
・yH
2
O
where Mn+
1/n
is either a metal ion or H+. These positive ions can be exchanged for others in a contacting electrolyte solution. H+
exchanged zeolites are particularly useful as solid acid catalysts.[2]

The term was originally coined in 1756 by Swedish mineralogist Axel Fredrik Cronstedt, who observed that rapidly heating a 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 ζέω (zéō), meaning "to boil" and λίθος (líthos), meaning "stone".[3]

Zeolites occur naturally, but are also produced industrially on a large scale. As of December 2018, 253 unique zeolite frameworks have been identified, and over 40 naturally occurring zeolite frameworks are known.[4][5] Every new zeolite structure that is obtained is examined by the International Zeolite Association Structure Commission (IZA-SC) and receives a three-letter designation.[6]

Characteristics edit

Properties edit

 
Microscopic structure of a zeolite (mordenite) framework, assembled from corner-sharing SiO
4
tetrahedra. Sodium is present as an extra-framework cation (in green). Si atoms can be partially replaced by Al or other tetravalent metals.

Zeolites are white solids with ordinary handling properties, like many routine aluminosilicate minerals, e.g. feldspar. They have the general formula MAlO2)(SiO2)x(H2O)y where M+ is usually H+ and Na+. The Si/Al ratio is variable, which provides a means to tune the properties. Zeolites with a Si/Al ratios higher than about 3 are classified as high-silica zeolites, which tend to be more hydrophobic. The H+ and Na+ can be replaced by diverse cations, because zeolites have ion exchange properties. The nature of the cations influences the porosity of zeolites.

Zeolites have microporous structures with a typical diameter of 0.3–0.8 nm. Like most aluminosilicates, the framework is formed by linking of aluminum and silicon atoms by oxides. This linking leads to a 3-dimensional network of Si-O-Al, Si-O-Si, and Al-O-Al linkages. The aluminum centers are negatively charged, which requires an accompanying cation. These cations are hydrated during the formation of the materials. The hydrated cations interrupt the otherwise dense network of Si-O-Al, Si-O-Si, and Al-O-Al linkage, leading to regular water-filled cavities. Because of the porosity of the zeolite, the water can exit the material through channels. Because of the rigidity of the zeolite framework, the loss of water does not result in collapse of the cavities and channels. This aspect – the ability to generate voids within the solid material – underpins the ability of zeolites to function as catalysts. They possess high physical and chemical stability due to the large covalent bonding contribution. They have excellent hydrophobicity and are suited for adsorption of bulky, hydrophobic molecules such as hydrocarbons. In addition to that, high-silica zeolites are H+
exchangeable, unlike natural zeolites, and are used as solid acid catalysts. The acidity is strong enough to protonate hydrocarbons and high-silica zeolites are used in acid catalysis processes such as fluid catalytic cracking in petrochemical industry.[7]

 
Zeolite Mordenite with some Si atoms substituted with Al atoms.


Framework structure edit

 
Three ways to represent the oxygen 4-membered ring structure of silicate compounds.
 
Comparison of framework structures of LTA-type zeolite (left) and FAU-type zeolite (right)

The structures of hundreds of zeolites have been determined. Most do not occur naturally. For each structure, the International Zeolite Association (IZA) gives a three-letter code called framework type code (FTC).[4] For example, the major molecular sieves, 3A, 4A and 5A, are all LTA (Linde Type A). Most commercially available natural zeolites are of the MOR, HEU or ANA-types.

An example of the notation of the ring structure of zeolite and other silicate materials is shown in the upper right figure. The middle figure shows a common notation using structural formula. The left figure emphasizes the SiO4 tetrahedral structure. Connecting oxygen atoms together creates a four-membered ring of oxygen (blue bold line). In fact, such a ring substructure is called four membered ring or simply four-ring. The figure on the right shows a 4-ring with Si atoms connected to each other, which is the most common way to express the topology of the framework.

The figure on the right compares the typical framework structures of LTA (left) and FAU (right). Both zeolites share the truncated octahedral structure (sodalite cage) (purple line). However, the way they are connected (yellow line) is different: in LTA, the four-membered rings of the cage are connected to each other to form a skeleton, while in FAU, the six-membered rings are connected to each other. As a result, the pore entrance of LTA is an 8-ring (0.41 nm[4]) and belongs to the small pore zeolite, while the pore entrance of FAU is a 12-ring (0.74 nm[4]) and belongs to the large pore zeolite, respectively. Materials with a 10-ring are called medium pore zeolites, a typical example being ZSM-5 (MFI).

Although more than 200 types of zeolites are known, only about 100 types of aluminosilicate are available. In addition, there are only a few types that can be synthesized in industrially feasible way and have sufficient thermal stability to meet the requirements for industrial use. In particular, the FAU (faujasite, USY), *BEA (beta), MOR (high-silica mordenite), MFI (ZSM-5), and FER (high-silica ferrierite) types are called the big five of high silica zeolites,[8] and industrial production methods have been established.

Porosity edit

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 "eight-ring" refers to a closed-loop that is built from eight tetrahedrally coordinated silicon (or aluminium) atoms and eight 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.

Isomorphous substitution edit

Isomorphous substitution of Si in zeolites can be possible for some heteroatoms such as titanium,[9] zinc[10] and germanium.[11] Al atoms in zeolites can be also structurally replaced with boron[12] and gallium.[13]

The silicoaluminophosphate type (AlPO molecular sieve),[14] in which Si is isomorphous with Al and P and Al is isomorphous with Si, and the gallogermanate[15] and others are known.

Natural occurrence edit

 
A form of thomsonite (one of the rarest zeolites) from India

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: 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.[citation needed]

Zeolites transform to other minerals under weathering, hydrothermal alteration or metamorphic conditions. Some examples:[16]

Gemstones edit

 
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. 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 displays a "cat's eye" effect (chatoyancy).[17]

Production edit

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 the use of structure directing agents (SDA) such as quaternary ammonium cations.[18]

Synthetic zeolites hold some key advantages over their natural analogs. 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.

Ore mining edit

 
Natrolite from Poland

As of 2016, 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).[19] 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. These materials are used for construction, e.g. dimension stone (as an altered volcanic tuff), lightweight aggregate, pozzolanic cement, and soil conditioners.[20]

Synthesis edit

 
Synthetic zeolite

Over 200 synthetic zeolites have been reported.[21] Most zeolites have aluminosilicate frameworks but some incorporate germanium, iron, gallium, boron, zinc, tin, and titanium.[22] Zeolite synthesis involves sol-gel-like processes. 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 the sol-gel process, other elements (metals, metal oxides) can be easily incorporated.

Applications edit

Zeolites are widely used as catalysts and sorbents.[23] Their well-defined pore structure and adjustable acidity make them highly active in a large variety of reactions.[24][2] In chemistry, zeolites are used as membranes to separate molecules (only molecules of certain sizes and shapes can pass through), and as traps for molecules so they can be analyzed.

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.[25]

Organic synthesis edit

In synthetic chemistry, homogeneous catalysts are preferred because of availability, low cost, and excellent catalytic activity as all the catalytic sites are readily available. However, these homogeneous catalysts have several disadvantages, such as being non-reusable, requiring more than a stoichiometric amount, and difficulty in separation and recovery. Some other drawbacks in its use include the potential dangers in handling, toxicity, corrosive nature, and disposal problems due to the acidic effluent. In addition to that, hydrolysis and purification of the resultant complex results in corrosive by-products. Research is ongoing into alternative heterogeneous solid catalysts which are stable, reusable, and nature-friendly, and which will also allow a better work up of reaction products. Among these different solid catalysts, zeolites were found to be superior due to their shape selectivity, thermal stability, and reusability.

Friedel–Crafts alkylation and acylations using zeolites as catalyst are common in organic synthesis.[2]

Ion-exchange, water purification and softening edit

Zeolites are widely used as ion-exchange beds in domestic and commercial water purification, softening, and other applications.

Evidence for the oldest known zeolite water purification filtration system occurs in the undisturbed sediments of the Corriental reservoir at the Maya city of Tikal, in northern Guatemala.[26]

Earlier, polyphosphates were used to soften hard water. The polyphosphates forms complex with metal ions like Ca2+ and Mg2+ to bind them up so that they could not interfere in cleaning process. However, when this phosphate rich water goes in main stream water, it results in eutrophication of water bodies and hence use of polyphosphate was replaced with use of a synthetic zeolite.

The largest single use for zeolite is the global laundry detergent market. Zeolites are used in laundry detergent as water softeners, removing Ca2+ and Mg2+ ions which would otherwise precipitate from the solution. The ions are retained by the zeolites which releases Na+ ions into the solution, allowing the laundry detergent to be effective in areas with hard water.[27]

Catalysis edit

Synthetic zeolites, like other mesoporous materials (e.g., MCM-41), are widely used as catalysts in the petrochemical industry, such as in fluid catalytic cracking and hydrocracking. Zeolites confine molecules into 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 isomerization, alkylation, and cracking.

Catalytic cracking uses a reactor and a regenerator. Feed is injected onto a 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 the 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 containing cobalt nanoparticles have applications in the recycling industry as a catalyst to break down polyethylene and polypropylene, two widely used plastics, into propane.[28]

Nuclear waste reprocessing edit

 
A researcher at Sandia National Laboratories examines vials of SOMS (Sandia Octahedral Molecular Sieve), a zeolite that shows potential for radioactive waste and industrial metals cleanup.

Zeolites have been used in advanced nuclear 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 the radioactive cesium-137 that was present in high levels.[29]

Gas separation and storage edit

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.

On-board oxygen generating systems (OBOGS) and oxygen concentrators use zeolites in conjunction with pressure swing adsorption to remove nitrogen from compressed air to supply oxygen for aircrews at high altitudes, as well as home and portable oxygen supplies.[30]

 
Animation of pressure swing adsorption, (1) and (2) showing alternating adsorption and desorption
I compressed air input A adsorption
O oxygen output D desorption
E exhaust

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.

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 four times greater than water.[31][non-primary source needed][32][33] Ultimately, the goal is to store heat both in industrial installations and in small combined heat and power plants such as those used in larger residential buildings.

Debbie Meyer Green Bags, a produce storage and preservation product, uses a form of zeolite as its active ingredient. The bags are lined with zeolite to adsorb ethylene, which is intended to slow the ripening process and extend the shelf life of produce stored in the bags.

Clinoptilolite has also been added to chicken food: the absorption of water and ammonia by the zeolite made the birds' droppings drier and less odoriferous, hence easier to handle.[34]

Zeolites are also used as a molecular sieve in cryosorption style vacuum pumps.[35]

Solar energy storage and use edit

Zeolites can be used to thermochemically store solar heat harvested from solar thermal collectors as first demonstrated by Guerra in 1978[36] and for adsorption refrigeration, as first demonstrated by Tchernev in 1974.[37] 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 form to a hydrated form make natural zeolites useful in harvesting waste heat and solar heat energy.[non-primary source needed]

Building materials edit

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 vapors. 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.[38] When added to lime mortars and lime-metakaolin mortars, synthetic zeolite pellets can act simultaneously as a pozzolanic material and a water reservoir.[39][40]

Cat litter edit

Non-clumping cat litter is often made of zeolite (or diatomite), one form of which, invented at MIT, can sequester the greenhouse gas methane from the atmosphere.[41]

Hemostatic agent edit

The original formulation of QuikClot brand hemostatic agent, which is used to stop severe bleeding,[42] contained zeolite granules. When in contact with blood, the granules would rapidly absorb water from the blood plasma, creating an exothermic reaction which generated heat. The absorption of water would also concentrate clotting factors present within the blood, causing the clot formation process to occur much faster than under normal circumstances, as shown in vitro.[43]

The 2022 formulation of QuikClot uses a nonwoven material impregnated with kaolin, an inorganic mineral activating Factor XII, in turn accelerating natural clotting.[44] Unlike the original zeolite formulation, kaolin does not exhibit any thermogenic properties.

Soil treatment edit

 
Mixing composted waste matter from wine production with zeolites
 
The microporous structure of the zeolites put into ground stabilizes water release and pH

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.

Aquaria edit

Pet stores market zeolites for use as filter additives in aquaria,[20] 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 into 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 can be replaced by other ions in solution, thus the take-up of nitrogen in ammonia, with the release of the sodium. A deposit near Bear River in southern Idaho is a fresh water variety (Na < 0.05%).[45] Southern hemisphere zeolites are typically formed in freshwater and have a high calcium content.[46]

Mineral species edit

 
A combination specimen of four zeolite species. The radiating natrolite crystals are protected in a pocket with associated stilbite. The matrix around and above the pocket is lined with small, pink-colored laumontite crystals. Heulandite is also present as a crystal cluster on the backside

The zeolite structural group (Nickel-Strunz classification) includes:[4][16][47][48][49]

  • 09.GA. – Zeolites with T5O10 units (T = combined Si and Al): the fibrous zeolites
  • 09.GB. – Chains of single connected 4-membered rings
  • 09.GC. – Chains of doubly connected 4-membered rings
  • 09.GD. – Chains of 6-membered rings: tabular zeolites
    • Chabazite framework (CHA): chabazite-series, herschelite, willhendersonite and SSZ-13
    • Faujasite framework (FAU): faujasite-series, Linde type X (zeolite X, X zeolites), Linde type Y (zeolite Y, Y zeolites)
    • Mordenite framework (MOR): maricopaite, mordenite
    • Offretite–wenkite subgroup 09.GD.25 (Nickel–Strunz, 10 ed): offretite (OFF), wenkite (WEN)
    • Bellbergite (TMA-E, Aiello and Barrer; framework type EAB), bikitaite (BIK), erionite-series (ERI), ferrierite (FER), gmelinite (GME), levyne-series (LEV), dachiardite-series (DAC), epistilbite (EPI)
  • 09.GE. – Chains of T10O20 tetrahedra (T = combined Si and Al)
  • Others
    • Cowlesite, pentasil (also known as ZSM-5, framework type MFI), tschernichite (beta polymorph A, disordered framework, BEA), Linde type A framework (zeolite A, LTA)

Computational study edit

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 observed. This problem is often referred to as "the bottleneck problem".[citation needed] Currently, several theories attempt to explain the reasoning behind this question.

  1. Zeolite synthesis research has primarily concentrated on hydrothermal methods; however, new zeolites may be synthesized using alternative methods. Synthesis methods that have started to gain use include microwave-assisted, post-synthetic modification, and steam.
  2. Geometric computer simulations have shown that the discovered zeolite frameworks possess a behavior known as "the flexibility window". This shows that there is a range in which the zeolite structure is "flexible" and can be compressed but retains the framework structure. It is suggested that if a framework does not possess this property then it cannot be feasibly synthesized.
  3. As zeolites are metastable, certain frameworks may be inaccessible as nucleation cannot occur because more stable and energetically favorable zeolites will form. Post-synthetic modification has been used to combat this issue with the ADOR method,[50] whereby frameworks can be cut apart into layers and bonded back together by either removing silica bonds or including them.
  4. Based on dense crystal model systems, the theory of crystallization via solute pre-nucleation clusters was developed.[51] Investigation of zeolite crystallization in hydrated silicate ionic liquids (HSIL) has shown that zeolites can nucleate via the condensation of ion-paired pre-nucleation clusters.[52] This line of research identified several connections between the synthesis medium liquid chemistry and important properties of zeolite crystals, such as the role of inorganic structure-directing agents in zeolite framework selection,[53] the role of ion-pairing on the zeolite molecular composition and topology,[54] and the role of liquid cation mobility on the zeolite crystal size and morphology.[55] Consequently, complex relations exist between the properties of zeolite synthesis media and the crystallizing zeolite, potentially explaining why only a small fraction of the hypothetical zeolite frameworks can be synthesized. While these relations are not yet fully understood, HSIL zeolite synthesis is an exceptional model system for zeolite science, providing opportunities to advance current understanding of the zeolite conundrum.

See also edit

  • Geopolymer – Polymeric Si–O–Al framework similar to zeolites but amorphous
  • List of minerals – List of minerals with Wikipedia articles
  • Hypothetical zeolite – combinatorial model of potential structures of the minerals known as zeolites
  • Adsorption – Phenomenon of surface adhesion
  • Solid sorbents for carbon capture – Solid materials that can adsorb carbon dioxide from air.
  • Pyrolysis – Thermal decomposition of materials at elevated temperatures in an inert atmosphere

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Further reading edit

  • The classic reference for the field has been Breck's book Zeolite Molecular Sieves: Structure, Chemistry, And Use.[1]
  • Sheppard RA (1973). "Zeolites in Sedimentary Rocks". In Brobst DA, Pratt WP (eds.). United States mineral resources. Professional Paper. Vol. 820. Washington, DC: USGS. pp. 689–695. doi:10.3133/pp820.
  • Clifton RA (1987). Natural and Synthetic Zeolites. Information Circular, 9140. Pittsburgh: USBM. OCLC 14932428.
  • Mumpton FA (1999). "La roca magica: Uses of natural zeolites in agriculture and industry". PNAS. 96 (7): 3463–3470. Bibcode:1999PNAS...96.3463M. doi:10.1073/pnas.96.7.3463. PMC 34179. PMID 10097058.
  • Monnier JB, Dupont M (1983). "Zeolite-water close cycle solar refrigeration; numerical optimisation and field-testing". Proc. Annu. Meet. - Am. Sect. Int. Sol. Energy Soc. 6: 181–185. OSTI 5126636. American Solar Energy Society meeting. 1 Jun 1983. Minneapolis, MN, USA{{cite journal}}: CS1 maint: postscript (link)
  • Newsam JM (1992). "Zeolites". In Cheetham AK, Day P (eds.). Solid State Chemistry. Vol. 2. Clarendon Press. ISBN 9780198551669.
  • Rhodes CJ (2007). "Zeolites: Physical Aspects and Environmental Applications". Annu. Rep. Prog. Chem. C. 103: 287–325. doi:10.1039/b605702k.
  •   This article incorporates public domain material from Zeolites (PDF). United States Geological Survey.

External links edit

  • International Zeolite Association
  • Database of zeolite pore characterizations 2014-05-24 at the Wayback Machine
  • Federation of European Zeolite Associations
  • British Zeolite Association
  • Bulk Zeolite
  • Database of Zeolite Structures
  1. ^ Breck DW (1973). Zeolite molecular sieves: structure, chemistry, and use. Wiley. ISBN 9780471099857.

zeolite, family, several, microporous, crystalline, aluminosilicate, materials, commonly, used, commercial, adsorbents, catalysts, they, mainly, consist, silicon, aluminium, oxygen, have, general, formula, alo2, sio2, where, either, metal, these, positive, ion. Zeolite is a family of several microporous crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts 1 They mainly consist of silicon aluminium oxygen and have the general formula Mn 1 n AlO2 SiO2 x yH2 O where Mn 1 n is either a metal ion or H These positive ions can be exchanged for others in a contacting electrolyte solution H exchanged zeolites are particularly useful as solid acid catalysts 2 The term was originally coined in 1756 by Swedish mineralogist Axel Fredrik Cronstedt who observed that rapidly heating a 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 zew zeō meaning to boil and li8os lithos meaning stone 3 Zeolites occur naturally but are also produced industrially on a large scale As of December 2018 update 253 unique zeolite frameworks have been identified and over 40 naturally occurring zeolite frameworks are known 4 5 Every new zeolite structure that is obtained is examined by the International Zeolite Association Structure Commission IZA SC and receives a three letter designation 6 Contents 1 Characteristics 1 1 Properties 1 2 Framework structure 1 3 Porosity 1 4 Isomorphous substitution 2 Natural occurrence 2 1 Gemstones 3 Production 3 1 Ore mining 3 2 Synthesis 4 Applications 4 1 Organic synthesis 4 2 Ion exchange water purification and softening 4 3 Catalysis 4 4 Nuclear waste reprocessing 4 5 Gas separation and storage 4 6 Solar energy storage and use 4 7 Building materials 4 8 Cat litter 4 9 Hemostatic agent 4 10 Soil treatment 4 11 Aquaria 5 Mineral species 6 Computational study 7 See also 8 References 9 Further reading 10 External linksCharacteristics editProperties edit nbsp Microscopic structure of a zeolite mordenite framework assembled from corner sharing SiO4 tetrahedra Sodium is present as an extra framework cation in green Si atoms can be partially replaced by Al or other tetravalent metals Zeolites are white solids with ordinary handling properties like many routine aluminosilicate minerals e g feldspar They have the general formula MAlO2 SiO2 x H2O y where M is usually H and Na The Si Al ratio is variable which provides a means to tune the properties Zeolites with a Si Al ratios higher than about 3 are classified as high silica zeolites which tend to be more hydrophobic The H and Na can be replaced by diverse cations because zeolites have ion exchange properties The nature of the cations influences the porosity of zeolites Zeolites have microporous structures with a typical diameter of 0 3 0 8 nm Like most aluminosilicates the framework is formed by linking of aluminum and silicon atoms by oxides This linking leads to a 3 dimensional network of Si O Al Si O Si and Al O Al linkages The aluminum centers are negatively charged which requires an accompanying cation These cations are hydrated during the formation of the materials The hydrated cations interrupt the otherwise dense network of Si O Al Si O Si and Al O Al linkage leading to regular water filled cavities Because of the porosity of the zeolite the water can exit the material through channels Because of the rigidity of the zeolite framework the loss of water does not result in collapse of the cavities and channels This aspect the ability to generate voids within the solid material underpins the ability of zeolites to function as catalysts They possess high physical and chemical stability due to the large covalent bonding contribution They have excellent hydrophobicity and are suited for adsorption of bulky hydrophobic molecules such as hydrocarbons In addition to that high silica zeolites are H exchangeable unlike natural zeolites and are used as solid acid catalysts The acidity is strong enough to protonate hydrocarbons and high silica zeolites are used in acid catalysis processes such as fluid catalytic cracking in petrochemical industry 7 nbsp Zeolite Mordenite with some Si atoms substituted with Al atoms Framework structure edit nbsp Three ways to represent the oxygen 4 membered ring structure of silicate compounds nbsp Comparison of framework structures of LTA type zeolite left and FAU type zeolite right The structures of hundreds of zeolites have been determined Most do not occur naturally For each structure the International Zeolite Association IZA gives a three letter code called framework type code FTC 4 For example the major molecular sieves 3A 4A and 5A are all LTA Linde Type A Most commercially available natural zeolites are of the MOR HEU or ANA types An example of the notation of the ring structure of zeolite and other silicate materials is shown in the upper right figure The middle figure shows a common notation using structural formula The left figure emphasizes the SiO4 tetrahedral structure Connecting oxygen atoms together creates a four membered ring of oxygen blue bold line In fact such a ring substructure is called four membered ring or simply four ring The figure on the right shows a 4 ring with Si atoms connected to each other which is the most common way to express the topology of the framework The figure on the right compares the typical framework structures of LTA left and FAU right Both zeolites share the truncated octahedral structure sodalite cage purple line However the way they are connected yellow line is different in LTA the four membered rings of the cage are connected to each other to form a skeleton while in FAU the six membered rings are connected to each other As a result the pore entrance of LTA is an 8 ring 0 41 nm 4 and belongs to the small pore zeolite while the pore entrance of FAU is a 12 ring 0 74 nm 4 and belongs to the large pore zeolite respectively Materials with a 10 ring are called medium pore zeolites a typical example being ZSM 5 MFI Although more than 200 types of zeolites are known only about 100 types of aluminosilicate are available In addition there are only a few types that can be synthesized in industrially feasible way and have sufficient thermal stability to meet the requirements for industrial use In particular the FAU faujasite USY BEA beta MOR high silica mordenite MFI ZSM 5 and FER high silica ferrierite types are called the big five of high silica zeolites 8 and industrial production methods have been established Porosity edit 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 eight ring refers to a closed loop that is built from eight tetrahedrally coordinated silicon or aluminium atoms and eight 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 Isomorphous substitution edit Isomorphous substitution of Si in zeolites can be possible for some heteroatoms such as titanium 9 zinc 10 and germanium 11 Al atoms in zeolites can be also structurally replaced with boron 12 and gallium 13 The silicoaluminophosphate type AlPO molecular sieve 14 in which Si is isomorphous with Al and P and Al is isomorphous with Si and the gallogermanate 15 and others are known Natural occurrence edit nbsp A form of thomsonite one of the rarest zeolites from IndiaSome 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 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 citation needed Zeolites transform to other minerals under weathering hydrothermal alteration or metamorphic conditions Some examples 16 The sequence of silica rich volcanic rocks commonly progresses from Clay quartz mordenite heulandite epistilbite stilbite thomsonite mesolite scolecite chabazite calcite citation needed The sequence of silica poor volcanic rocks commonly progresses from Cowlesite levyne offretite analcime thomsonite mesolite scolecite chabazite calcite Gemstones edit nbsp Polished thomsoniteThomsonites 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 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 displays a cat s eye effect chatoyancy 17 Production editIndustrially 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 the use of structure directing agents SDA such as quaternary ammonium cations 18 Synthetic zeolites hold some key advantages over their natural analogs 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 Ore mining edit nbsp Natrolite from PolandAs 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 19 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 These materials are used for construction e g dimension stone as an altered volcanic tuff lightweight aggregate pozzolanic cement and soil conditioners 20 Synthesis edit nbsp Synthetic zeoliteOver 200 synthetic zeolites have been reported 21 Most zeolites have aluminosilicate frameworks but some incorporate germanium iron gallium boron zinc tin and titanium 22 Zeolite synthesis involves sol gel like processes 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 the sol gel process other elements metals metal oxides can be easily incorporated Applications editZeolites are widely used as catalysts and sorbents 23 Their well defined pore structure and adjustable acidity make them highly active in a large variety of reactions 24 2 In chemistry zeolites are used as membranes to separate molecules only molecules of certain sizes and shapes can pass through and as traps for molecules so they can be analyzed 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 25 Organic synthesis edit In synthetic chemistry homogeneous catalysts are preferred because of availability low cost and excellent catalytic activity as all the catalytic sites are readily available However these homogeneous catalysts have several disadvantages such as being non reusable requiring more than a stoichiometric amount and difficulty in separation and recovery Some other drawbacks in its use include the potential dangers in handling toxicity corrosive nature and disposal problems due to the acidic effluent In addition to that hydrolysis and purification of the resultant complex results in corrosive by products Research is ongoing into alternative heterogeneous solid catalysts which are stable reusable and nature friendly and which will also allow a better work up of reaction products Among these different solid catalysts zeolites were found to be superior due to their shape selectivity thermal stability and reusability Friedel Crafts alkylation and acylations using zeolites as catalyst are common in organic synthesis 2 Ion exchange water purification and softening edit Zeolites are widely used as ion exchange beds in domestic and commercial water purification softening and other applications Evidence for the oldest known zeolite water purification filtration system occurs in the undisturbed sediments of the Corriental reservoir at the Maya city of Tikal in northern Guatemala 26 Earlier polyphosphates were used to soften hard water The polyphosphates forms complex with metal ions like Ca2 and Mg2 to bind them up so that they could not interfere in cleaning process However when this phosphate rich water goes in main stream water it results in eutrophication of water bodies and hence use of polyphosphate was replaced with use of a synthetic zeolite The largest single use for zeolite is the global laundry detergent market Zeolites are used in laundry detergent as water softeners removing Ca2 and Mg2 ions which would otherwise precipitate from the solution The ions are retained by the zeolites which releases Na ions into the solution allowing the laundry detergent to be effective in areas with hard water 27 Catalysis edit Synthetic zeolites like other mesoporous materials e g MCM 41 are widely used as catalysts in the petrochemical industry such as in fluid catalytic cracking and hydrocracking Zeolites confine molecules into 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 isomerization alkylation and cracking Catalytic cracking uses a reactor and a regenerator Feed is injected onto a 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 the 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 containing cobalt nanoparticles have applications in the recycling industry as a catalyst to break down polyethylene and polypropylene two widely used plastics into propane 28 Nuclear waste reprocessing edit nbsp A researcher at Sandia National Laboratories examines vials of SOMS Sandia Octahedral Molecular Sieve a zeolite that shows potential for radioactive waste and industrial metals cleanup Zeolites have been used in advanced nuclear 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 the radioactive cesium 137 that was present in high levels 29 Gas separation and storage edit 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 On board oxygen generating systems OBOGS and oxygen concentrators use zeolites in conjunction with pressure swing adsorption to remove nitrogen from compressed air to supply oxygen for aircrews at high altitudes as well as home and portable oxygen supplies 30 nbsp Animation of pressure swing adsorption 1 and 2 showing alternating adsorption and desorption I compressed air input A adsorption O oxygen output D desorption E exhaustZeolite 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 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 four times greater than water 31 non primary source needed 32 33 Ultimately the goal is to store heat both in industrial installations and in small combined heat and power plants such as those used in larger residential buildings Debbie Meyer Green Bags a produce storage and preservation product uses a form of zeolite as its active ingredient The bags are lined with zeolite to adsorb ethylene which is intended to slow the ripening process and extend the shelf life of produce stored in the bags Clinoptilolite has also been added to chicken food the absorption of water and ammonia by the zeolite made the birds droppings drier and less odoriferous hence easier to handle 34 Zeolites are also used as a molecular sieve in cryosorption style vacuum pumps 35 Solar energy storage and use edit Zeolites can be used to thermochemically store solar heat harvested from solar thermal collectors as first demonstrated by Guerra in 1978 36 and for adsorption refrigeration as first demonstrated by Tchernev in 1974 37 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 form to a hydrated form make natural zeolites useful in harvesting waste heat and solar heat energy non primary source needed Building materials edit 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 vapors 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 38 When added to lime mortars and lime metakaolin mortars synthetic zeolite pellets can act simultaneously as a pozzolanic material and a water reservoir 39 40 Cat litter edit Non clumping cat litter is often made of zeolite or diatomite one form of which invented at MIT can sequester the greenhouse gas methane from the atmosphere 41 Hemostatic agent edit The original formulation of QuikClot brand hemostatic agent which is used to stop severe bleeding 42 contained zeolite granules When in contact with blood the granules would rapidly absorb water from the blood plasma creating an exothermic reaction which generated heat The absorption of water would also concentrate clotting factors present within the blood causing the clot formation process to occur much faster than under normal circumstances as shown in vitro 43 The 2022 formulation of QuikClot uses a nonwoven material impregnated with kaolin an inorganic mineral activating Factor XII in turn accelerating natural clotting 44 Unlike the original zeolite formulation kaolin does not exhibit any thermogenic properties Soil treatment edit nbsp Mixing composted waste matter from wine production with zeolites nbsp The microporous structure of the zeolites put into ground stabilizes water release and pH 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 Aquaria edit Pet stores market zeolites for use as filter additives in aquaria 20 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 into 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 can be replaced by other ions in solution thus the take up of nitrogen in ammonia with the release of the sodium A deposit near Bear River in southern Idaho is a fresh water variety Na lt 0 05 45 Southern hemisphere zeolites are typically formed in freshwater and have a high calcium content 46 Mineral species edit nbsp A combination specimen of four zeolite species The radiating natrolite crystals are protected in a pocket with associated stilbite The matrix around and above the pocket is lined with small pink colored laumontite crystals Heulandite is also present as a crystal cluster on the backsideThe zeolite structural group Nickel Strunz classification includes 4 16 47 48 49 09 GA Zeolites with T5O10 units T combined Si and Al the fibrous zeolites Natrolite framework NAT gonnardite natrolite mesolite paranatrolite scolecite tetranatrolite Edingtonite framework EDI edingtonite kalborsite Thomsonite framework THO thomsonite series 09 GB Chains of single connected 4 membered rings Analcime framework ANA analcime leucite pollucite wairakite Laumontite LAU yugawaralite YUG goosecreekite GOO montesommaite MON 09 GC Chains of doubly connected 4 membered rings Phillipsite framework PHI harmotome phillipsite series Gismondine framework GIS amicite gismondine garronite gobbinsite Boggsite BOG merlinoite MER mazzite series MAZ paulingite series PAU perlialite Linde type L framework zeolite L LTL 09 GD Chains of 6 membered rings tabular zeolites Chabazite framework CHA chabazite series herschelite willhendersonite and SSZ 13 Faujasite framework FAU faujasite series Linde type X zeolite X X zeolites Linde type Y zeolite Y Y zeolites Mordenite framework MOR maricopaite mordenite Offretite wenkite subgroup 09 GD 25 Nickel Strunz 10 ed offretite OFF wenkite WEN Bellbergite TMA E Aiello and Barrer framework type EAB bikitaite BIK erionite series ERI ferrierite FER gmelinite GME levyne series LEV dachiardite series DAC epistilbite EPI 09 GE Chains of T10O20 tetrahedra T combined Si and Al Heulandite framework HEU clinoptilolite heulandite series Stilbite framework STI barrerite stellerite stilbite series Brewsterite framework BRE brewsterite series Others Cowlesite pentasil also known as ZSM 5 framework type MFI tschernichite beta polymorph A disordered framework BEA Linde type A framework zeolite A LTA Computational study editComputer 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 observed This problem is often referred to as the bottleneck problem citation needed Currently several theories attempt to explain the reasoning behind this question Zeolite synthesis research has primarily concentrated on hydrothermal methods however new zeolites may be synthesized using alternative methods Synthesis methods that have started to gain use include microwave assisted post synthetic modification and steam Geometric computer simulations have shown that the discovered zeolite frameworks possess a behavior known as the flexibility window This shows that there is a range in which the zeolite structure is flexible and can be compressed but retains the framework structure It is suggested that if a framework does not possess this property then it cannot be feasibly synthesized As zeolites are metastable certain frameworks may be inaccessible as nucleation cannot occur because more stable and energetically favorable zeolites will form Post synthetic modification has been used to combat this issue with the ADOR method 50 whereby frameworks can be cut apart into layers and bonded back together by either removing silica bonds or including them Based on dense crystal model systems the theory of crystallization via solute pre nucleation clusters was developed 51 Investigation of zeolite crystallization in hydrated silicate ionic liquids HSIL has shown that zeolites can nucleate via the condensation of ion paired pre nucleation clusters 52 This line of research identified several connections between the synthesis medium liquid chemistry and important properties of zeolite crystals such as the role of inorganic structure directing agents in zeolite framework selection 53 the role of ion pairing on the zeolite molecular composition and topology 54 and the role of liquid cation mobility on the zeolite crystal size and morphology 55 Consequently complex relations exist between the properties of zeolite synthesis media and the crystallizing zeolite potentially explaining why only a small fraction of the hypothetical zeolite frameworks can be synthesized While these relations are not yet fully understood HSIL zeolite synthesis is an exceptional model system for zeolite science providing opportunities to advance current understanding of the zeolite conundrum See also editGeopolymer Polymeric Si O Al framework similar to zeolites but amorphous List of minerals List of minerals with Wikipedia articles Hypothetical zeolite combinatorial model of potential structures of the minerals known as zeolitesPages displaying wikidata descriptions as a fallback Adsorption Phenomenon of surface adhesion Solid sorbents for carbon capture Solid materials that can adsorb carbon dioxide from air Pages displaying wikidata descriptions as a fallback Pyrolysis Thermal decomposition of materials at elevated temperatures in an inert atmosphereReferences edit Zeolite Structure GRACE com W R Grace amp Co 2006 Archived from the original on 15 February 2009 Retrieved 8 Feb 2019 a b c Nayak Yogeesha N Nayak Swarnagowri Nadaf Y F Shetty Nitinkumar S Gaonkar Santosh L 2020 Zeolite Catalyzed Friedel Crafts Reactions A Review Letters in Organic Chemistry 17 7 491 506 doi 10 2174 1570178616666190807101012 S2CID 201222323 Cronstedt AF 1756 Natural zeolite and minerals Svenska Vetenskaps Akademiens Handlingar Stockholm 17 120 a b c d e Database of Zeolite Structures iza structure org International Zeolite Association 2017 Retrieved 24 May 2021 Minerals Arranged by the New Dana Classification webmineral com Retrieved 8 Feb 2019 News from the Structure Commission IZA Structure Commission 2018 Retrieved 8 Feb 2018 Greenwood Norman N Earnshaw Alan 1997 Chemistry of the Elements 2nd ed Butterworth Heinemann ISBN 978 0 08 037941 8 An Overview on Zeolite Shaping Technology and Solutions to Overcome Diffusion Limitations Catalysts 8 163 2018 US patent 4410501A Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides issued 1979 12 21 US patent 2016243531A1 Processes for preparing zincoaluminosilicates with aei cha and gme topologies and compositions derived therefrom issued 2015 02 24 Shamzhy Mariya V Eliasova Pavla Vitvarova Dana Opanasenko Maksym V Firth Daniel S Morris Russell E 2016 Post Synthesis Stabilization of Germanosilicate Zeolites ITH IWW and UTL by Substitution of Ge for Al Chemistry A European Journal 22 48 17377 17386 doi 10 1002 chem 201603434 hdl 10023 11880 PMID 27754569 US patent 5187132A Preparation of borosilicate zeolites issued 1993 02 16 Incorporation of Gallium into Zeolites Syntheses Properties and Catalytic Application Chem Rev 100 2303 2405 2000 Crystal Structure of Tetrapropylammonium Hydroxide Aluminium Phosphate Number 5 ACS Sym Ser 218 109 118 1983 Hydrothermal synthesis and structural characterization of zeolite like structures based on gallium and aluminium germanates J Am Chem Soc 120 13389 13397 1998 a b Tschernich RW 1992 Zeolites of the World Geoscience Press ISBN 9780945005070 Dietrich RV 2005 Thomsonite GemRocks Retrieved 2 Oct 2013 Rollmann LD Valyocsik EW Shannon RD 1995 Zeolite Molecular Sieves In Murphy DW Interrante LV eds Inorganic Syntheses Nonmolecular Solids Vol 30 New York Wiley amp Sons pp 227 234 doi 10 1002 9780470132616 ch43 ISBN 9780470132616 Zeolites natural PDF USGS Mineral Commodity Summaries 2011 Archived PDF from the original on 2011 06 08 Retrieved 8 Feb 2019 a b Virta RL 2011 2009 Minerals Yearbook Zeolites PDF USGS Archived PDF from the original on 2011 06 08 Retrieved 8 Feb 2019 Earl DJ Deem MW 2006 Toward a Database of Hypothetical Zeolite Structures Ind Eng Chem Res 45 16 5449 5454 doi 10 1021 ie0510728 ISSN 0888 5885 Szostak R 1998 Molecular Sieves Principles of Synthesis and Identification Van Nostrand Reinhold Electrical Computer Science and Engineering Series Springer ISBN 9780751404807 P Chatterjee Y Han T Kobayashi K Verma M Mais R Behera T Johnson T Prozorov J Evans I I Slowing W Huang 2023 Capturing Rare Earth Elements by Synthetic Aluminosilicate MCM 22 Mechanistic Understanding of Yb III Capture ACS Appl Mater Interfaces doi 10 1021 acsami 3c14560 Bhatia S 1989 Zeolite Catalysts Principles and Applications Boca Raton CRC Press ISBN 9780849356285 Auerbach SM Carrado KA Dutta PK eds 2003 Handbook of Zeolite Science and Technology Boca Raton CRC Press p 16 ISBN 9780824740207 Tankersley K B Dunning N P Carr C et al Zeolite water purification at Tikal an ancient Maya city in Guatemala Sci Rep 10 18021 2020 https doi org 10 1038 s41598 020 75023 7 Chemistry3 introducing inorganic organic and physical chemistry Andrew Burrows Oxford Oxford University Press 2009 p 253 ISBN 978 0 19 927789 6 OCLC 251213960 a href Template Cite book html title Template Cite book cite book a CS1 maint others link New process could enable more efficient plastics recycling MIT News Massachusetts Institute of Technology Retrieved 2023 04 22 The Associated Press 16 Apr 2011 Level of Radioactive Materials Rises Near Japan Plant NYTimes ISSN 0362 4331 On Board Oxygen Generating System OBOGS Honeywell com Honeywell International Inc Archived from the original on 10 September 2011 Retrieved 9 Feb 2019 Compact and flexible thermal storage Fraunhofer Research News Fraunhofer Gesellschaft 1 Jun 2012 Pirsaheb Meghdad Hossaini Hiwa Amini Jila 2021 Operational parameters influenced on biogas production in zeolite anaerobic baffled reactor for compost leachate treatment Journal of Environmental Health Science amp Engineering 19 2 1743 1751 doi 10 1007 s40201 021 00729 3 PMC 8617091 PMID 34900303 Druzyanova Varvara Petrova Sofya Khiterkheeva Nadezhda Bardamova Irina Gergenova Tatyana 2020 Rudoy D Ignateva S eds The use of zeolites for biogas purification in agricultural production E3S Web of Conferences 175 12012 doi 10 1051 e3sconf 202017512012 Mumpton FA 1985 Ch VIII Using Zeolites in Agriculture PDF In Elfring C ed Innovative Biological Technologies for Lesser Developed Countries Washington DC US Congress Office of Technology Assessment LCCN 85600550 Archived PDF from the original on 2022 10 10 Ventura G Risegari L 2007 The Art of Cryogenics Low Temperature Experimental Techniques Elsevier p 17 ISBN 9780080444796 U S Pat No 4 269 170 Adsorption Solar Heating and Storage System Filed April 27 1978 Inventor John M Guerra U S Patent No 4 034 569 Filed November 4 1974 Inventor Dimiter I Tchernev Dypayan J 2007 Clinoptilolite a promising pozzolan in concrete PDF A New Look at an Old Pozzolan 29th ICMA Conference Quebec City Canada Construction Materials Consultants Inc pp 168 206 Archived PDF from the original on 2022 10 10 Retrieved 7 Oct 2013 Andrejkovicova S Ferraz E Velosa AL et al 2012 Air Lime Mortars with Incorporation of Sepiolite and Synthetic Zeolite Pellets PDF Acta Geodynamica et Geomaterialia 9 1 79 91 Archived PDF from the original on 2022 10 10 Ferraza E Andrejkovicova S Velosa AL et al 2014 Synthetic zeolite pellets incorporated to air lime metakaolin mortars mechanical properties Construction amp Building Materials 69 243 252 doi 10 1016 j conbuildmat 2014 07 030 Dezember Ryan May 14 2022 Cat Litter Could Be Antidote for Climate Change Researchers Say via www wsj com Rhee P Brown C Martin M et al 2008 QuikClot use in trauma for hemorrhage control case series of 103 documented uses The Journal of Trauma and Acute Care Surgery 64 4 1093 9 doi 10 1097 TA 0b013e31812f6dbc PMID 18404080 S2CID 24827908 Li Jing Cao Wei Lv Xiao xing et al 2013 03 01 Zeolite based hemostat QuikClot releases calcium into blood and promotes blood coagulation in vitro Acta Pharmacologica Sinica 34 3 367 372 doi 10 1038 aps 2012 159 ISSN 1671 4083 PMC 4002488 PMID 23334236 QuikClot for Military US Dept of Defense Hemostatic Dressing of Choice Teleflex Inc 2022 Retrieved 2023 10 01 Hongting Z Vance GF Ganjegunte GK et al 2008 Use of zeolites for treating natural gas co produced waters in Wyoming USA Desalination 228 1 3 263 276 doi 10 1016 j desal 2007 08 014 Wang Shaobin Peng Yuelian 2009 10 09 Natural zeolites as effective adsorbents in water amp wastewater treatment PDF Chemical Engineering Journal 156 1 11 24 doi 10 1016 j cej 2009 10 029 Archived PDF from the original on 2022 10 10 Retrieved 2019 07 13 Database of Mineral Properties IMA Retrieved 9 Feb 2019 Nickel Strunz Classification Primary Groups 10th ed mindat org Retrieved 10 Feb 2019 First EL Gounaris CE Wei J et al 2011 Computational characterization of zeolite porous networks An automated approach Phys Chem Chem Phys 13 38 17339 17358 Bibcode 2011PCCP 1317339F doi 10 1039 C1CP21731C PMID 21881655 Roth WJ Nachtigall P Morris RE et al 2013 A family of zeolites with controlled pore size prepared using a top down method Nat Chem 5 7 628 633 Bibcode 2013NatCh 5 628R doi 10 1038 nchem 1662 hdl 10023 4529 ISSN 1755 4330 PMID 23787755 Gebauer Denis Kellermeier Matthias Gale Julian D Bergstrom Lennart Colfen Helmut January 23 2014 Pre nucleation clusters as solute precursors in crystallisation Chemical Society Reviews 43 7 2348 2371 doi 10 1039 C3CS60451A hdl 20 500 11937 6133 PMID 24457316 Pellens Nick Doppelhammer Nikolaus Radhakrishnan Sambhu Asselman Karel Chandran C Vinod Vandenabeele Dries Jakoby Bernhard Martens Johan A Taulelle Francis Reichel Erwin K Breynaert Eric Kirschhock Christine E A 2022 Nucleation of Porous Crystals from Ion Paired Prenucleation Clusters Chemistry of Materials 34 16 7139 7149 doi 10 1021 acs chemmater 2c00418 PMC 9404542 PMID 36032557 Asselman Karel Pellens Nick Radhakrishnan Sambhu Chandran C Vinod Martens Johan A Taulelle Francis Verstraelen Toon Hellstrom Matti Breynaert Eric Kirschhock Christine E A August 4 2021 Super ions of sodium cations with hydrated hydroxide anions inorganic structure directing agents in zeolite synthesis Materials Horizons 8 9 2576 2583 doi 10 1039 D1MH00733E hdl 1854 LU 8740859 PMID 34870303 S2CID 238722345 Asselman Karel Pellens Nick Thijs Barbara Doppelhammer Nikolaus Haouas Mohamed Taulelle Francis Martens Johan A Breynaert Eric Kirschhock Christine E A 2022 Ion Pairs in Aluminosilicate Alkali Synthesis Liquids Determine the Aluminium Content and Topology of Crystallizing Zeolites Chemistry of Materials 34 16 7150 7158 doi 10 1021 acs chemmater 2c00773 PMC 9404546 PMID 36032556 Pellens Nick Doppelhammer Nikolaus Thijs Barbara Jakoby Bernhard Reichel Erwin K Taulelle Francis Martens Johan A Breynaert Eric Kirschhock Christine E A 2022 A zeolite crystallisation model confirmed by in situ observation Faraday Discussions 235 162 182 Bibcode 2022FaDi 235 162P doi 10 1039 D1FD00093D PMID 35660805 S2CID 245465624 Further reading editThe classic reference for the field has been Breck s book Zeolite Molecular Sieves Structure Chemistry And Use 1 Sheppard RA 1973 Zeolites in Sedimentary Rocks In Brobst DA Pratt WP eds United States mineral resources Professional Paper Vol 820 Washington DC USGS pp 689 695 doi 10 3133 pp820 Clifton RA 1987 Natural and Synthetic Zeolites Information Circular 9140 Pittsburgh USBM OCLC 14932428 Mumpton FA 1999 La roca magica Uses of natural zeolites in agriculture and industry PNAS 96 7 3463 3470 Bibcode 1999PNAS 96 3463M doi 10 1073 pnas 96 7 3463 PMC 34179 PMID 10097058 Monnier JB Dupont M 1983 Zeolite water close cycle solar refrigeration numerical optimisation and field testing Proc Annu Meet Am Sect Int Sol Energy Soc 6 181 185 OSTI 5126636 American Solar Energy Society meeting 1 Jun 1983 Minneapolis MN USA a href Template Cite journal html title Template Cite journal cite journal a CS1 maint postscript link Newsam JM 1992 Zeolites In Cheetham AK Day P eds Solid State Chemistry Vol 2 Clarendon Press ISBN 9780198551669 Rhodes CJ 2007 Zeolites Physical Aspects and Environmental Applications Annu Rep Prog Chem C 103 287 325 doi 10 1039 b605702k nbsp This article incorporates public domain material from Zeolites PDF United States Geological Survey External links edit nbsp Wikimedia Commons has media related to Zeolite nbsp Scholia has a topic profile for Zeolite International Zeolite Association Database of zeolite pore characterizations Archived 2014 05 24 at the Wayback Machine The Synthesis Commission of the International Zeolite Association Federation of European Zeolite Associations British Zeolite Association Bulk Zeolite Database of Zeolite Structures Breck DW 1973 Zeolite molecular sieves structure chemistry and use Wiley ISBN 9780471099857 Retrieved from https en wikipedia org w index php title Zeolite amp oldid 1194593740, wikipedia, wiki, book, books, library,

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