TOPICAL

o EDITORIAL/TOPICAL
o NEWS
o EMERGING CONTAMINANTS
o SMALL SYSTEMS
o WATER REUSE
o WATER SCARCITY
o PRESS RELEASES
 DEALERS
o BUSINESS
o CERTIFICATION
o LEGISLATION & REGULATIONS
o TOP DEALERS
o TRAINING
o TRENDS & FORECASTS
 WATER TREATMENT
o DISINFECTION
o FAUCETS & FITTINGS
o FILTRATION
o GROUNDWATER
o MEMBRANES
o POU/POE
o PUMPS
o REVERSE OSMOSIS
o SOFTENING/CONDITIONING
o TESTING
 COMMERCIAL WATER
o COOLING WATER TREATMENT
o HEALTHCARE WATER TREATMENT
o HOTEL WATER TREATMENT
o LEGIONELLA PREVENTION

JUSTIN RAMSEY
MAY 30, 2012

FACEBOOKTWITTERLINKEDIN

EXTENDING THE LIFE OF RESIN FOR WATER

SOFTENERS
Cleaning options to reduce resin fouling

Updated 10/28/19

Water softener resin is extremely porous, which is beneficial because it allows for more surface area
to capture calcium and other metals in source water. Surprisingly, 99% of ion exchange actually
happens in the interior of the bead. Resin beads, ranging in size from 16 to 50 mesh, are abused
daily during the backwash process and by contaminants in the source water. Resin could last much
longer in these hostile environments with a few fairly inexpensive solutions.

Resin Basics
Resin is designed to change the chemical makeup of minerals, which makes them cling to the resin
beads. In the exchange, the resin bead loses sodium and/or potassium ions. Just before the resin
becomes completely saturated with calcium or magnesium, the unit should be set to regenerate.
This allows a sodium-rich brine solution (or potassium permanganate for greensand applications) to
rinse away the minerals stuck to the resin beads and restore them to peak efficiency—at least in
theory.
Resin Killers

Resin life varies based on several factors, such as the type of resin used, the minerals or oxidants
present in the source water and the regeneration cycle. Some resin manufacturers see gel-type, 8%
softening resin life as a 10- to 15-year event. Because cation resin is essentially porous plastic
beads, it is highly susceptible to chloramines and chlorine degradation. The presence of 2-ppm
residual chlorine in a water system can cut the life expectancy of a standard softening resin in half.

Chlorine and chloramines attack the divinylbenzene (DVB) in resin, which causes it to swell and take
on moisture. DVB is the ingredient in resin that gives it a hard, porous shape. As DVB breaks down,
the pores and channels inside the beads break down and close up. The results include pressure loss
and resin that is so mushy it can be crushed easily between two fingers.

Over-brining and fast rinses with freshwater also can cause resin to foul. In situations in which the
brine has more than 45% salinity, water is drawn out of the bead due to osmosis and the bead
shrinks. In a fast-rinse scenario, water enters the beads at such a quick pace that it causes them to
swell and crack. As the beads break down into smaller sizes, they are flushed more easily down the
drain during regeneration. Most newer models only allow for slow-rinse cycles to prevent this from
occurring.

Resin Foulers

Organic fouling is the most common and expensive form of resin fouling and degradation. Well water
is typically low in organic materials, but surface waters contain hundreds of parts per million of
natural and manmade organic matter.

Natural organics are formed from decaying materials and are usually acidic and have an odor. The
most typical natural contaminants include tannins, oils, tannic acid and fulvic acid. These
contaminants plug the interiors of beads, causing a fish eye effect. If these organics remain on the
resin, they break down the strong base of the beads until they are no longer active. At this stage,
cleaning the resin can return some of the lost capacity, but the ability to remove silica and carbonic
acid will be lost.

In situations in which iron or manganese is present, organic fouling is accelerated. Ferrous iron
exchanges ions and attaches itself to resin the same way as hardness minerals. However, a brine
solution alone will not dislodge iron ions from resin beads. The iron is oxidized as air is introduced
into the system, and the now-ferric iron attaches itself to the surface of the bead as well. The beads
will stick to one another, causing channeling. This restricts the flow of water over the resin to specific
arteries that form over time in the resin tank, reducing the exchange capacity of the tank to as low as
10%. Manganese fouls resin in the same manner as iron.

Resin Cleaning

With municipal and occasionally well water supplies relying on chlorine for microbial control, a
carbon filter is highly recommended ahead of a water softener. With levels of 2 ppm of residual
chlorine or chloramines, the resin life will double with a prefiltration system. This process also will
help reduce the amount of organic compounds introduced into the brine tank.

Resin cleaning will prevent the buildup of organic compounds and even can clear built-up iron from
the pores of beads. There are several methods and products available for continuous resin cleaning.
One option is powder cleaners, such as Pro Products’ Softener Mate or Ban T, which are designed
specifically to clean oils and organic compounds. Powder cleaners can be layered in between each
bag of salt or poured directly down the brine well to treat extremely fouled resin.

There are also multiple liquid resin cleaners on the market, such as Pro Products’ Pro Res Care or
Res Up, which can be used in an automatic feeder system to deliver precise amounts of cleaning
solution to rid resin of organic compounds and limited amounts of iron. Both liquid and powder resin
cleaners eliminate the fish eye effect on beads, clearing out the porous surfaces so they can again
be used to soften water.

High-iron resin cleaning requires more strength to change the chemical property of the iron.
Cleaning products such as Pro Products’ Pro Rust Out are formulated to strip iron from the resin
beads and eliminate channeling. In situations in which iron levels are more than 2 ppm, the cleaner
can be layered between each bag of salt or poured down the brine well to treat extremely fouled
resin. Because an iron-fouled unit can have a reduced capacity of up to 90%, using a high-iron resin
cleaner can greatly extend the life of resin and save on salt and water costs.

Open main menu


 







Search

Ion-exchange resin
 Language
 Watch
 Edit
An ion-exchange resin or ion-exchange polymer is a resin or polymer that acts as a medium
for ion exchange. It is an insoluble matrix (or support structure) normally in the form of small
(0.25–0.5 mm radius) microbeads, usually white or yellowish, fabricated from
an organic polymer substrate. The beads are typically porous, providing a large surface area on
and inside them the trapping of ions occurs along with the accompanying release of other ions,
and thus the process is called ion exchange. There are multiple types of ion-exchange resin. Most
commercial resins are made of polystyrene sulfonate.[1]

Ion-exchange resin beads

Ion-exchange resin beads

Ion-exchange resins are widely used in different separation, purification, and decontamination

processes. The most common examples are water softening and water purification. In many
cases ion-exchange resins were introduced in such processes as a more flexible alternative to the
use of natural or artificial zeolites. Also, ion-exchange resins are highly effective in the biodiesel
filtration process.
Types of resinsEdit
Most typical ion-exchange resins are based on crosslinked polystyrene. The actual ion-
exchanging sites are introduced after polymerisation. Additionally, in the case of polystyrene,
crosslinking is introduced by copolymerisation of styrene and a few percent of divinylbenzene.
Crosslinking decreases ion-exchange capacity of the resin and prolongs the time needed to
accomplish the ion-exchange processes but improves the robustness of the resin. Particle size
also influences the resin parameters; smaller particles have larger outer surface, but cause
larger head loss in the column processes.[2]
Besides being made as bead-shaped materials, ion-exchange resins are also produced as
membranes. These ion-exchange membranes, which are made of highly cross-linked ion-
exchange resins that allow passage of ions, but not of water, are used for electrodialysis.
Four main types of ion-exchange resins differ in their functional groups:
 strongly acidic, typically featuring sulfonic acid groups, e.g. sodium polystyrene
sulfonate or polyAMPS,
 strongly basic, typically featuring quaternary amino groups, for
example, trimethylammonium groups, e.g. polyAPTAC),
 weakly acidic, typically featuring carboxylic acid groups,
  weakly basic, typically featuring primary, secondary, and/or tertiary amino groups,
e.g. polyethylene amine.

Specialised ion-exchange resins are also known such as chelating resins (iminodiacetic

acid, thiourea-based resins, and many others).
Anion resins and cation resins are the two most common resins used in the ion-exchange process.
While anion resins attract negatively charged ions, cation resins attract positively charged ions.

Anion resinsEdit
Anion resins may be either strongly or weakly basic. Strongly basic anion resins maintain their
negative charge across a wide pH range, whereas weakly basic anion resins are neutralized at
higher pH levels.[3] Weakly basic resins do not maintain their charge at a high pH because they
undergo deprotonation.[3] They do, however, offer excellent mechanical and chemical stability.
This, combined with a high rate of ion exchange, make weakly base anion resins well suited for
the organic salts.
For anion resins, regeneration typically involves treatment of the resin with a strongly basic
solution, e.g. aqueous sodium hydroxide. During regeneration, the regenerant chemical is passed
through the resin, and trapped negative ions are flushed out, renewing the resin exchange
capacity.

Cation-exchange resin[4]Edit
Formula: R−H acidic

The cation exchange method removes the hardness of water but induces acidity in it, which is
further removed in the next stage of treatment of water by passing this acidic water through
an anion exchange process.
Reaction:

R−H + M+ = R−M + H+.

Anion-exchange resin[4]Edit
Formula: NR4+OH−
Often these are styrene–divinylbenzene copolymer resins that have quaternary ammonium
cations as an integral part of the resin matrix.
Reaction:

NR4+OH− + HCl = NR4+Cl− + H2O.

Anion-exchange chromatography makes use of this principle to extract and purify materials

from mixtures or solutions.
UsesEdit
Water softeningEdit
Main article: Water softening
In this application, ion-exchange resins are used to replace the magnesium and calcium ions
found in hard water with sodium ions. When the resin is fresh, it contains sodium ions at its
active sites. When in contact with a solution containing magnesium and calcium ions (but a low
concentration of sodium ions), the magnesium and calcium ions preferentially migrate out of
solution to the active sites on the resin, being replaced in solution by sodium ions. This process
reaches equilibrium with a much lower concentration of magnesium and calcium ions in solution
than was started with.

Idealised image of water-softening process, involving replacement of calcium ions in water with sodium ions donated by a
cation-exchange resin

The resin can be recharged by washing it with a solution containing a high concentration of
sodium ions (e.g. it has large amounts of common salt (NaCl) dissolved in it). The calcium and
magnesium ions migrate from the resin, being replaced by sodium ions from the solution until a
new equilibrium is reached. The salt is used to recharge an ion-exchange resin, which itself is
used to soften the water.
Water purificationEdit
Main article: Purified water

In this application, ion-exchange resins are used to remove poisonous (e.g. copper) and

hazardous metal (e.g. lead or cadmium) ions from solution, replacing them with more innocuous
ions, such as sodium and potassium.
Few ion-exchange resins remove chlorine or organic contaminants from water – this is usually
done by using an activated charcoal filter mixed in with the resin. There are some ion-exchange
resins that do remove organic ions, such as MIEX (magnetic ion-exchange) resins. Domestic
water purification resin is not usually recharged – the resin is discarded when it can no longer be
used.
Water of highest purity is required for electronics, scientific experiments, production of
superconductors, and nuclear industry, among others. Such water is produced using ion-
exchange processes or combinations of membrane and ion-exchange methods.
Ion exchange in metal separationEdit

A drum of yellowcake

Ion-exchange processes are used to separate and purify metals, including

separating uranium from plutonium and other actinides, including thorium;
and lanthanum, neodymium, ytterbium, samarium, lutetium, from each other and the
other lanthanides. There are two series of rare-earth metals, the lanthanides and the actinides.
Members of each family have very similar chemical and physical properties. Ion exchange was
for many years the only practical way to separate the rare earths in large quantities. This
application was developed in the 1940s by Frank Spedding. Subsequently, solvent extraction has
mostly supplanted use of ion-exchange resins except for the highest-purity products.
A very important case is the PUREX process (plutonium-uranium extraction process), which is
used to separate the plutonium and the uranium from the spent fuel products from a nuclear
reactor, and to be able to dispose of the waste products. Then, the plutonium and uranium are
available for making nuclear-energy materials, such as new reactor fuel and nuclear weapons.
Ion-exchange beads are also an essential component in in-situ leach uranium mining. In-situ
recovery involves the extraction of uranium-bearing water (grading as low as 0.05% U3O8) through
boreholes. The extracted uranium solution is then filtered through the resin beads. Through an
ion-exchange process, the resin beads attract uranium from the solution. Uranium-loaded resins
are then transported to a processing plant, where U3O8 is separated from the resin beads,
and yellowcake is produced. The resin beads can then be returned to the ion-exchange facility,
where they are reused.
The ion-exchange process is also used to separate other sets of very similar chemical elements,
such as zirconium and hafnium, which incidentally is also very important for the nuclear
industry. Zirconium is practically transparent to free neutrons, used in building reactors, but
hafnium is a very strong absorber of neutrons, used in reactor control rods.
CatalysisEdit
Ion exchange resins are used in organic synthesis, e.g. for esterification and hydrolysis. Being
high surface area and insoluble, they are suitable for vapor-phase and liquid-phase reactions.
Examples can be found where basic (OH−-form) of ion exchange resins are used to neutralize of
ammonium salts[5] and convert quaternary ammonium halides to hydroxides.[6] Acidic (H+-form)
ion exchange resins have been used as solid acid catalysts for scission of ether protecting groups.
[7] and for rearrangement reactions.[8]
Juice purificationEdit
Ion-exchange resins are used in the manufacture of fruit juices such as orange and cranberry
juice, where they are used to remove bitter-tasting components and so improve the flavor. This
allows tart or poorer-tasting fruit sources to be used for juice production.

Sugar manufacturingEdit
Ion-exchange resins are used in the manufacturing of sugar from various sources. They are used
to help convert one type of sugar into another type of sugar, and to decolorize and purify sugar
syrups.
PharmaceuticalsEdit
Ion-exchange resins are used in the manufacturing of pharmaceuticals, not only
for catalyzing certain reactions, but also for isolating and purifying pharmaceutical active
ingredients. Three ion-exchange resins, sodium polystyrene sulfonate, colestipol,
and cholestyramine, are used as active ingredients. Sodium polystyrene sulfonate is a strongly
acidic ion-exchange resin and is used to treat hyperkalemia. Colestipol is a weakly basic ion-
exchange resin and is used to treat hypercholesterolemia. Cholestyramine is a strongly basic ion-
exchange resin and is also used to treat hypercholesterolemia. Colestipol and cholestyramine are
known as bile acid sequestrants.
Ion-exchange resins are also used as excipients in pharmaceutical formulations such as tablets,
capsules, gums, and suspensions. In these uses the ion-exchange resin can have several different
functions, including taste-masking, extended release, tablet disintegration,
increased bioavailability, and improving the chemical stability of the active ingredients.
Selective polymeric chelators have been proposed for maintenance therapy of some pathologies,
where chronic ion accumulation occurs, such as Wilson disease (where copper accumulation
occurs)[9] or hereditary hemochromatosis (iron overload, where iron accumulation occurs)[10][11]
[12] These polymers or particles have a negligible or null systemic biological availability and they
are designed to form stable complexes with Fe2+ and Fe3+ in the GIT and thus limiting the uptake
of these ions and their long-term accumulation. Although this method has only a limited efficacy,
unlike small-molecular chelators (deferasirox, deferiprone, or deferoxamine), such an approach
may have only minor side effects in sub-chronic studies.[12] Interestingly, the simultaneous
chelation of Fe2+ and Fe3+ increases the treatment efficacy.[12]
See alsoEdit
 Polyelectrolyte
 Water softening

NotesEdit
1. ^ François Dardel and Thomas V. Arden "Ion Exchangers" in Ullmann's Encyclopedia of
Industrial Chemistry, 2008, Wiley-VCH, Weinheim. doi:10.1002/14356007.a14_393.pub2.
2. ^ IUPAC "strongly discourages" the use of the term "ion-exchange resin" to refer to an
ion-exchange polymer, but the usage remains common: International Union of Pure and Applied
Chemistry (2004), "Definitions of Terms Relating to Reactions of Polymers and to Functional
Polymeric Materials (IUPAC Recommendations 2003)"  (PDF), Pure Appl. Chem., 76 (4): 889–
906, doi:10.1351/pac200476040889
3. ^ a b Wikibooks:Proteomics/Protein Separations - Chromatography/Ion exchange#Anion
Exchangers.
 4. ^ a b Vagliasindi, Federico G. A.; Belgiorno, Vincenzo; Napoli, Rodolfo M. A. (1998-01-
01), Gavasci, Renato; Zandaryaa, Sarantuyaa (eds.), "WATER TREATMENT IN REMOTE AND
RURAL AREAS: A CONCEPTUAL SCREENING PROTOCOL FOR APPROPRIATE POU/POE
TECHNOLOGIES", Environmental Engineering and Renewable Energy, Oxford: Elsevier,
pp. 329–336, doi:10.1016/b978-0-08-043006-5.50049-5, ISBN 978-0-08-043006-5,
retrieved 2020-10-27
5. ^ Cal Y. Meyers a.nd Leonard E. Miller (1952). "ε-Aminocaproic Acid". Org. Synth. 32:
13. doi:10.15227/orgsyn.032.0013.
6. ^ Carl Kaiser and Joseph Weinstock (1976). "Alkenes Via Hofmann Elimination: Use of
Ion-exchange Resin for Preparation of Quaternary Ammonium Hydroxides: Diphenylmethyl
Vinyl Ether". Org. Synth. 55: 3. doi:10.15227/orgsyn.055.0003.
7. ^ R. A. Earl, L. B. Townsend (1981). "Methyl 4-Hydroxy-2-butynoate". Org. Synth. 60:
81. doi:10.15227/orgsyn.060.0081.
8. ^ David G. Hilmey, Leo A. Paquette (2007). "1,3-Dichloroacetone as a Cyclopropanone
Equivalent: 5-oxaspiro[3.4]octan-1-one". Org. Synth. 84: 156. doi:10.15227/orgsyn.084.0156.
9. ^ Mattová, Jana; Poučková, Pavla; Kučka, Jan; Škodová, Michaela; Vetrík, Miroslav;
Štěpánek, Petr; Urbánek, Petr; Petřík, Miloš; Nový, Zbyněk; Hrubý, Martin (2014). "Chelating
polymeric beads as potential therapeutics for Wilson's disease". European Journal of
Pharmaceutical Sciences. 62: 1–7. doi:10.1016/j.ejps.2014.05.002. ISSN 0928-0987.
10. ^ Polomoscanik, Steven C.; Cannon, C. Pat; Neenan, Thomas X.; Holmes-Farley, S.
Randall; Mandeville, W. Harry; Dhal, Pradeep K. (2005). "Hydroxamic Acid-Containing
Hydrogels for Nonabsorbed Iron Chelation Therapy: Synthesis, Characterization, and Biological
Evaluation". Biomacromolecules. 6 (6): 2946–2953. doi:10.1021/bm050036p. ISSN 1525-
7797. PMID 16283713.
11. ^ Qian, Jian; Sullivan, Bradley P.; Peterson, Samuel J.; Berkland, Cory (2017).
"Nonabsorbable Iron Binding Polymers Prevent Dietary Iron Absorption for the Treatment of
Iron Overload". ACS Macro Letters. 6 (4): 350–
353. doi:10.1021/acsmacrolett.6b00945. ISSN 2161-1653.
12. ^ a b c Groborz, Ondřej; Poláková, Lenka; Kolouchová, Kristýna; Švec, Pavel;
Loukotová, Lenka; Miriyala, Vijay Madhav; Francová, Pavla; Kučka, Jan; Krijt, Jan; Páral,
Petr; Báječný, Martin; Heizer, Tomáš; Pohl, Radek; Dunlop, David; Czernek, Jiří; Šefc, Luděk;
Beneš, Jiří; Štěpánek, Petr; Hobza, Pavel; Hrubý, Martin (2020). "Chelating Polymers for
Hereditary Hemochromatosis Treatment". Macromolecular Bioscience:
2000254. doi:10.1002/mabi.202000254. ISSN 1616-5187. PMID 32954629.

Further readingEdit
 "Ion Exchange Chemistry and Operation". Remco Engineering. Archived from the original on
2014-02-20. Retrieved 2014-05-16.
 Friedrich G. Helfferich (1962). Ion Exchange. Courier Dover Publications. ISBN 978-0-486-
68784-1.
 Ion Exchangers (K. Dorfner, ed.), Walter de Gruyter, Berlin, 1991.
 C. E. Harland, Ion exchange: Theory and Practice, The Royal Society of Chemistry, Cambridge,
1994.
 Ion exchange (D. Muraviev, V. Gorshkov, A. Warshawsky), M. Dekker, New York, 2000.
 A. A. Zagorodni, Ion Exchange Materials: Properties and Applications, Elsevier, Amsterdam,
2006.
  Alexandratos S D . Ion-Exchange Resins: A Retrospective from Industrial and Engineering
Chemistry Research. Industrial & Engineering Chemistry Research, 2009.
 Catalyst system comprising an ion exchange resin and a dimethyl thiazolidine promoter,
Hasyagar U K , Mahalingam R J , Kishan G, WO 2012.

Last edited 2 months ago by Bibeyjj

RELATED ARTICLES
 Ion exchange
Exchange of ions between an electrolyte solution and a solid
 Polystyrene sulfonate
 Potassium binder

Content is available under CC BY-SA 3.0 unless otherwise noted.

 Privacy policy
 

 Terms of Use
 Desktop

Open main menu










Search

Zeolite
 Language
 Watch
 Edit
Learn more
 This article needs additional citations for verification.

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".[2] The classic reference for the field
has been Breck's book Zeolite Molecular Sieves: Structure, Chemistry, And Use.[3]

Natural zeolite with a U.S. penny for scale

Zeolites occur naturally but are also produced industrially on a large scale. As of
December 2018, 245 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 and receives a three
letter designation.[6]
Properties and occurrenceEdit

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

Microscopic structure of a zeolite (mordenite) framework, assembled from  tetrahedra. Sodium is present as an
extra-framework cation (in green).

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
2Al
2Si
3O
10·2H2O, the formula for natrolite. These cation exchanged zeolites possess different acidity
and catalyse several acid catalysis.[7][8][9]
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 ( and ) 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.
Zeolites transform to other minerals under weathering, hydrothermal
alteration or metamorphic conditions. Some examples:[10]
  The sequence of silica-rich volcanic rocks commonly progresses from:
o Clay → quartz → mordenite–heulandite → epistilbite → stilbite → thomsonite–
mesolite-scolecite → chabazite → calcite.[citation needed]
 The sequence of silica-poor volcanic rocks commonly progresses from:
o Cowlesite → levyne–offretite → analcime → thomsonite–mesolite-scolecite →
chabazite → calcite.

ProductionEdit
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.[11]
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 occurrenceEdit

Natrolite from Poland

Conventional open-pit mining techniques are used to mine natural zeolites. The overburden

is removed to allow access to the ore. The ore may be blasted or stripped for processing by
using tractors equipped with ripper blades and front-end loaders. In processing, the ore is
crushed, dried, and milled. The milled ore may be air-classified as to particle size and
shipped in bags or bulk. The crushed product may be screened to remove fine material when
a granular product is required, and some pelletized products are produced from fine
material.
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).[12] 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.[13]
Artificial synthesisEdit

Synthetic zeolite

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.[14] 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.[15] 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 conundrumEdit
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.

1. 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.
 2. 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 then it cannot be
feasibly synthesised.
3. 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, [16] whereby
frameworks can be cut apart into layers and bonded back together by either removing silica
bonds or including them.

Uses of zeolitesEdit
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.[17]
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 were discovered to help silver naturally emit light, which may compete with
fluorescent lights or LEDs.[18]
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.
[19]
IndustryEdit
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 isomerisation, 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 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
the radioactive caesium that was present in high levels.[20]
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.[21] 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.
Solar energy storage and useEdit
Zeolites can be used to thermochemically store solar heat harvested from solar thermal
collectors as first taught by Guerra in 1978[22] and for adsorption refrigeration, as first
taught by Tchernev in 1974[23]. 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. Zeolite manufactured by an Indian Company
namely M/s. G M Biochem is suitable for the purpose.
Commercial and domesticEdit
Zeolites are also used as a molecular sieve in cryosorption style vacuum pumps.[24]
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.[25] When added to lime mortars and lime-
metakaolin mortars, synthetic zeolite pellets can act simultaneously as a pozzolanic material
and a water reservoir.[26][27]
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.
 GemstonesEdit

Polished thomsonite

Thomsonites, one of the rarer zeolite minerals, have been collected as gemstones from a
series of lava flows along Lake Superior in Minnesota and, to a lesser degree, in Michigan,
U.S.. 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).[28]
BiologicalEdit

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
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.[29]
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,[30] contains a
calcium-loaded form of zeolite found in kaolin clay.[31]
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 and less odoriferous, hence easier to handle.[32]
Pet stores market zeolites for use as filter additives in aquaria,[13] 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 takeup 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%).[33] Southern hemisphere zeolites are typically formed in freshwater and have a high
calcium content.[34]
Zeolite mineral speciesEdit
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][10][35][36][37]

 09.GA. - Zeolites with T5O10 units (T = combined Si and Al) – the fibrous zeolites
o Natrolite framework
(NAT): gonnardite, natrolite, mesolite, paranatrolite, scolecite, tetranatrolite
oEdingtonite framework (EDI): edingtonite, kalborsite
oThomsonite framework (THO): thomsonite-series
 09.GB. - Chains of single connected 4-membered rings

oAnalcime framework (ANA): analcime, leucite, pollucite, wairakite

oLaumontite (LAU), yugawaralite (YUG), goosecreekite (GOO), montesommaite 
(MON)
 09.GC. - Chains of doubly connected 4-membered rings

oPhillipsite framework (PHI): harmotome, phillipsite-series

oGismondine framework (GIS): amicite, gismondine, garronite, gobbinsite
oBoggsite (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

o Chabazite framework (CHA): chabazite-

series, herschelite, willhendersonite and SSZ-13
o Faujasite framework (FAU): faujasite-series, Linde type X (zeolite X, X
zeolites), Linde type Y (zeolite Y, Y zeolites)
o Mordenite framework (MOR): maricopaite, mordenite
o Offretite–wenkite subgroup 09.GD.25 (Nickel–Strunz, 10
ed): offretite (OFF), wenkite (WEN)
o 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)
o Heulandite framework (HEU): clinoptilolite, heulandite-series
o Stilbite framework (STI): barrerite, stellerite, stilbite-series
o Brewsterite framework (BRE): brewsterite-series
 Others
o Cowlesite, pentasil (also known as ZSM-5, framework type
MFI), tschernichite (beta polymorph A, disordered framework, BEA), Linde type
A framework (zeolite A, LTA)

See alsoEdit
 Geopolymer, the amorphous alumino-silicate equivalent of zeolite
 List of minerals – A list of minerals for which there are articles on Wikipedia
 Hypothetical zeolite
 Adsorption – Process resulting from the attraction of atoms, ions, or molecules from a gas,
liquid, or solution sticking to a surface
 Solid sorbents for carbon capture
  Pyrolysis – Thermal decomposition of materials at elevated temperatures in an inert
atmosphere

ReferencesEdit
1. ^ "Zeolite Structure". GRACE.com. W. R. Grace & Co. 2006. Archived from the
original on 15 February 2009. Retrieved 8 Feb 2019.
2. ^ Cronstedt AF (1756). "Natural zeolite and minerals". Svenska Vetenskaps
Akademiens Handlingar Stockholm. 17: 120.
3. ^ Breck DW (1973). Zeolite molecular sieves: structure, chemistry, and use.
Wiley. ISBN 9780471099857.
4. ^ a b "Database of Zeolite Structures". iza-structure.org. International Zeolite
Association. 2017. Retrieved 8 Feb 2019.
5. ^ "Minerals Arranged by the New Dana Classification". webmineral.com. Retrieved 8
Feb 2019.
6. ^ "News from the Structure Commission". IZA Structure Commission. 2018.
Retrieved 8 Feb2018.
7. ^ Marakatti VS, Halgeri AB (2015). "Metal ion-exchanged zeolites as highly active
solid acid catalysts for the green synthesis of glycerol carbonate from glycerol". RSC
Adv. 5 (19): 14286–14293. doi:10.1039/C4RA16052E. ISSN 2046-2069.
8. ^ Marakatti VS, Halgeri AB, Shanbhag GV (2014). "Metal ion-exchanged zeolites as
solid acid catalysts for the green synthesis of nopol from Prins reaction". Catal. Sci.
Technol. 4 (11): 4065–4074. doi:10.1039/C4CY00596A. ISSN 2044-
4761. S2CID 94555012.
9. ^ Marakatti VS, Rao PV, Choudary NV, et al. (2014). "Influence of Alkaline Earth
Cation Exchanged X-Zeolites Towards Ortho-Selectivity in Alkylation of Aromatics: Hard-
Soft-Acid-Base Concept". Advanced Porous Materials. 2(4): 221–
229(9). doi:10.1166/apm.2014.1079.
10. ^ a b Tschernich RW (1992). Zeolites of the World. Geoscience
Press. ISBN 9780945005070.
11. ^ Rollmann LD, Valyocsik EW, Shannon RD (1995). "Zeolite Molecular Sieves". In
Murphy DW, Interrante LV (eds.). Inorganic Syntheses: Nonmolecular Solids. Inorganic
Syntheses. 30. New York: Wiley & Sons. pp. 227–
234. doi:10.1002/9780470132616.ch43. ISBN 9780470132616.
12. ^ "Zeolites (natural)"  (PDF). USGSMineral Commodity Summaries. 2011.
Retrieved 8 Feb 2019.
13. ^ a b Virta RL (2011). "2009 Minerals Yearbook - Zeolites"  (PDF). USGS.
Retrieved 8 Feb 2019.
14. ^ 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.
15. ^ Szostak R (1998). Molecular Sieves - Principles of Synthesis and Identification. Van
Nostrand Reinhold Electrical/Computer Science and Engineering Series.
Springer. ISBN 9780751404807.
16. ^ 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.
17. ^ Bhatia S (1989). Zeolite Catalysts: Principles and Applications. Boca Raton: CRC
Press. ISBN 9780849356285.
18. ^ Nelson B (2018). "Add another strange property to the list of silver's bizarre
traits". MNN. Narrative Content Group. Retrieved 9 Feb 2019.
19. ^ "On-Board Oxygen Generating System (OBOGS)". Honeywell.com. Honeywell
International Inc. Archived from the original on 10 September 2011. Retrieved 9 Feb 2019.
20. ^ The Associated Press (16 Apr 2011). "Level of Radioactive Materials Rises Near
Japan Plant". NYTimes. ISSN 0362-4331.
21. ^ "Compact and flexible thermal storage". Fraunhofer Research News. Fraunhofer-
Gesellschaft. 1 Jun 2012.
22. ^ U.S. Pat. No. 4,269,170, "Adsorption Solar Heating and Storage System," Filed
April 27, 1978, Inventor: John M. Guerra
23. ^ U.S. Patent No. 4,034,569, Filed Nov. 4, 1974, Inventor: Dimiter I. Tchernev
24. ^ Ventura G, Risegari L (2007). The Art of Cryogenics: Low-Temperature
Experimental Techniques. Elsevier. p. 17. ISBN 9780080444796.
25. ^ 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. Retrieved 7 Oct 2013.
26. ^ Andrejkovičová 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.
27. ^ Ferraza E, Andrejkovičová S, Velosa AL, et al. (2014). "Synthetic zeolite pellets
incorporated to air lime–metakaolin mortars: mechanical properties". Construction &
Building Materials. 69: 243–252. doi:10.1016/j.conbuildmat.2014.07.030.
28. ^ Dietrich RV (2005). "Thomsonite". GemRocks. Retrieved 2 Oct 2013.
29. ^ Auerbach SM, Carrado KA, Dutta PK, eds. (2003). Handbook of Zeolite Science
and Technology. Boca Raton: CRC Press. p. 16. ISBN 9780824740207.
30. ^ Rhee P, Brown C, Martin M, et al. (2008). "QuikClot use in trauma for hemorrhage
control: case series of 103 documented uses". J. Trauma. 64 (4): 1093–
9. doi:10.1097/TA.0b013e31812f6dbc. PMID 18404080. S2CID 24827908.
31. ^ Rowe A (2018). "Nanoparticles Help Gauze Stop Gushing Wounds". Wired. Condé
Nast. Retrieved 1 Nov 2013.
32. ^ 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.
33. ^ 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.
34. ^ Wang, Shaobin; Peng, Yuelian (2009-10-09). "Natural zeolites as effective
adsorbents in water & wastewater treatment"  (PDF). Chemical Engineering
Journal. 156 (1): 11–24. doi:10.1016/j.cej.2009.10.029. Retrieved 2019-07-13.
35. ^ "Database of Mineral Properties". IMA. Retrieved 9 Feb 2019.
36. ^ "Nickel-Strunz Classification - Primary Groups 10th ed". mindat.org. Retrieved 10
Feb 2019.
37. ^ 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 218816
55.

  This article incorporates public domain material from the United States Geological

Survey document: "Zeolites"  (PDF).
Further readingEdit
 Sheppard RA (1973). "Zeolites in Sedimentary Rocks". In Brobst DA, Pratt WP (eds.). United
States mineral resources. Professional Paper. 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 1
0097058.
 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
 Newsam JM (1992). "Zeolites". In Cheetham AK, Day P (eds.). Solid State Chemistry. 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.

External linksEdit
Wikimedia Commons has media related
to Zeolite.

Scholia has a topic profile for Zeolite.

 International Zeolite Association

 Database of zeolite pore characterizations
 The Synthesis Commission of the International Zeolite Association
 Federation of European Zeolite Associations
 British Zeolite Association
 Database of Zeolite Structures

Last edited 16 days ago by Monkbot

RELATED ARTICLES
 Molecular sieve
 Clinoptilolite
 Zeolite occurrences in Idaho

Content is available under CC BY-SA 3.0 unless otherwise noted.

 Privacy policy
 
 Terms of Use
 Desktop