What is it Zeolite?

Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents and catalysts.[1] 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 ζέω (zéō), meaning "to boil" and λίθος (líthos), meaning "stone". The classic reference for the field has been Zeolite molecular sieves: structure, chemistry, and use by Donald W. Breck.

 

Zeolites occur naturally but are also produced industrially on a large scale. As of September 2016, 232 unique zeolite frameworks have been identified, and over 40 naturally occurring zeolite frameworks are known.Every new zeolite structure that is obtained has to be approved by the International Zeolite Association Structure Commission and receives a three letter designation.

 

 

Propiertes and occurrence

 

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: Na2Al2Si3O10·2H2O, the formula for natrolite.

 

Natural zeolites form where volcanic rocks and ash layers react with alkaline groundwater. Zeolites also crystallize in post-depositional environments over periods ranging from thousands to millions of years in shallow marine basins. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, metals, quartz, or other zeolites. For this reason, naturally occurring zeolites are excluded from many important commercial applications where uniformity and purity are essential.

 

Zeolites are the aluminosilicate members of the family of microporous solids known as "molecular sieves" mainly consisting 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 effects, including strain induced by the bonding between units that are needed to produce the overall structure, or coordination of some of the oxygen atoms of the rings to cations within the structure. Therefore, the pores in many zeolites are not cylindrical.

 

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

 

The sequence of silica-rich volcanic rocks commonly progresses from:

Clay → quartz → mordenite–heulandite → epistilbite → stilbite → thomsonite–mesolite-scolecite → chabazite → calcite.

The sequence of silica-poor volcanic rocks commonly progresses from:

Cowlesite → levyne–offretite → analcime → thomsonite–mesolite-scolecite → chabazite → calcite.

 

 

Production

 

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.

 

 

Natural occurrence

 

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 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

 

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 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.

 

 

Artificial synthesis

 

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, however research is ongoing to understand the chemistry that would allow us to make these theoretical structures. 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.

 

 

The Zeolite conundrum

 

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.

 

Zeolite synthesis research has primarily been concentrating 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, steam.

Geometric computer simulations have shown that the discovered zeolite frameworks possess a behaviour known as 'The Flexibility Window'. This shows that there is a range in which the zeolite structure is 'flexible' and can be compressed but retain the framework structure. It is suggested that if a framework does not possess this property than it cannot be feasibly synthesised.

As zeolites are metastable, certain frameworks may be inaccessible as nucleation cannot occur because more stable and energetically favourable zeolites will form. Post-synthetic modification has been used to combat this issue with the ADOR method, whereby frameworks can be cut apart into layers and bonded back together by either removing silica bonds or including them.

 

 

 

 

                           WIKIPEDIA

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