Zeolites are eco-friendly alternatives to many products The largest application of the synthetic zeolites is the production of home laundry detergent powders, then goes the production of catalysts and adsorbents Natural zeolites which dominate the global market, are consumed in concrete, water treatment and pet litter sectors North America, Western Europe and Japan zeolites markets are mature and will post moderate growth The other regions demand will increase more noticeably, especially in Asia Pacific Zeolites Market Review is a source for detailed information on the market situation. The Lecture contains descriptive and analytical parts, enriched with tables and figures for national and global markets. Market forecasts for the next five years complete the Lecture.

1. ZEOLITES
2016- 2017
by
Hassan Z. Harraz
hharraz2006@yahoo.com
DOI: 10.13140/RG.2.2.34536.47365

2. Outlines:
• Zeolites are eco-friendly alternatives to many products
• The largest application of the synthetic zeolites is the production of home laundry
detergent powders, then goes the production of catalysts and adsorbents
• Natural zeolites which dominate the global market, are consumed in concrete, water
treatment and pet litter sectors
• North America, Western Europe and Japan zeolites markets are mature and will post
moderate growth
• The other regions demand will increase more noticeably, especially in Asia Pacific
• Zeolites Market Review is a source for detailed information on the market situation.
• The Lecture contains descriptive and analytical parts, enriched with tables and figures
for national and global markets. Market forecasts for the next five years complete the
Lecture.
2

3. • 1. ZEOLITES
• 1.1. Description
• 1.2. Application spheres
• 1.3. Worldwide resources
• 1.4. Substitutes
• 1.5. Environment issues
• 2. WORLD ZEOLITES
PRODUCTION
• 2.1. Zeolites production in 2011-2016
• 2.2. Profiles of major manufacturers
• 3. GLOBAL ZEOLITES DEMAND
• 3.1. Demand dynamics in 2011-2016
• 3.2. Zeolites consumption structure
➢ detergent powders
➢ catalysts
➢ adsorbents
➢ etc.
3
• 3.3. Zeolites demand by region
➢ Asia Pacific
➢ Europe
➢ North America
➢ Middle East and Africa
➢ Others
• 4. MARKET OF ZEOLITES
• 4.1. ASIA PACIFIC MARKET OF ZEOLITES
• 4.1.1. China
• 4.1.2. Japan
• 4.1.3. South Korea
• 4.2. NORTH AMERICAN MARKET OF ZEOLITES
• 4.2.1. USA
• 4.3. MIDDLE EAST MARKET OF ZEOLITES
• 4.3.1. Jordan
• 4.3.2. Turkey
• 5. ZEOLITES MARKET FORECAST UP TO 2027
• 5.1. Zeolites industry trends up to 2027
• 5.2. Supply forecast, projects
• 5.3. Demand forecast, downstream industries prospects

4. ZEOLITES
• Some aluminosilicates lose water when heated to forms a porous structure with a
large surface area.
• These aluminosilicates are called ZEOLITES.
• Zeolites are also known as Permutits.

5. What are zeolites?
• Zeolites are hydrated aluminosilicate minerals made from interlinked
tetrahedra of alumina (AlO4) and silica (SiO4).
• In simpler words, they're solids with a relatively open, three-dimensional
crystal structure built from the elements aluminum, oxygen, and silicon,
with alkali or alkaline-Earth metals (such as sodium, potassium, and
magnesium) plus water molecules trapped in the gaps between them.
• Zeolites form with many different crystalline structures, which have large
open pores (sometimes referred to as cavities) in a very regular
arrangement and roughly the same size as small molecules.
• Cavities (or Pores) occupied by cations and water molecules, both
of which have considerable freedom of movement, permitting
ion exchange and reversible dehydration. This definition places it
in the class of materials known as "molecular sieves."
• The pores in dehydrated zeolite are 6 Å in size, while those of a
typical silica gel average about 50 Å, and activated carbon
averages 105 Å.
5

6. Zeolites
• Tectosilicates, a crystalline structure characterized by a framework of linked
tetrahedra, each consisting of four O atoms surrounded by a cation.
• This framework open cavities in the form of channels and cages. These channels
are usually occupied by H2O, but large enough to allow the passage of guest
species.
• 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.
6

7. Zeolites
• The general chemical composition of a zeolite is:
Mn
x/nSi1-xAlxO2 · yH2O
Where M = e.g. Na+, K+, Li+, Ag+, NH4+, H+, Ca2+, Ba2+…
❖ This means that the Si/Al ratio is larger than 1 and that x is smaller than 0.5
❖ This rule is not always obeyed! (High aluminium e.g. Si/Al = 0.5)
❖ High silica and pure silica zeolites have been synthesized
Characteristics of zeolites:
1) Crystal System: triclinic
2) Physical properties: Color: Colorless, white, yellow, pink, redStreak: white; Transparent to translucent; Luster:
vitreous; Fracture: irregular/uneven; Soft to moderately hard, Moh's Hardness: 4-5, Low density
3) Tectosilicates, i.e. three dimensional structure built from tetrahedra. Some silicon atoms have been replaced by
aluminium, i.e. the (Si+Al)/O = ½. (Tetrahedra usually denoted T-atoms).
4) Loewensteins rule imposes a limit to the amount of aluminium which may be substituted into the framework: Number
of Al-O-Al may be present in tectosilicates (i.e., This means that only half of the silicon atoms may be substituted by
aluminium).
5) Open framework structure built from TO4-tetrahedra, containing pores and voids. The structure and porosity is periodic
(i.e. crystalline materials). The pores have molecular dimensions.
6) Counter ions (cations) are present in order to compensate for the negative framework charge created by aluminium
substitution. The counter ions are situated in the pores and voids, and are usually mobile.
7) In the voids and pores are also water molecules (zeolitic water). One measure of the porosity is the amount of
adsorbed water. The water molecules are also present in the pores and voids, and may (in many cases) be removed by
heating and readsorbed at lower temperatures.
8) Zeolites have a porous structure that can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+ and
others.
9) These positive ions are rather loosely held and can readily be exchanged for others in a contact solution.
7

8. Zeolite

9. Types of Zeolite
 Industrially speaking, the term zeolite includes natural silicate zeolites, synthetic
materials, and phosphate minerals that have a zeolite like structure
 Zeolites are of two types:
1) Natural zeolite :
➢ There are about 40 naturally occurring zeolites, forming in both volcanic and
sedimentary rocks; according to the US Geological Survey,
➢ Most common zeolite minerals are Analcime, Chabazite, Clinoptilite, Mordenite,
Natrolite, Heulandite, Phillipsite, and Stilbite.
➢ Natural zeolite are non-porous.
➢ for example, Natrolite ,Na2O.Al2O3.xSiO2.yH2O.
2) Synthetic zeolite :
➢ Synthetic (Artificial) zeolites (around 150) have been designed for specific
purposes, the best known of which are zeolite A (commonly used as a laundry
detergent), zeolites X and Y (two different types of faujasites, used for catalytic
cracking), and the petroleum catalyst ZSM-5 (a branded name for pentasil-
zeolite).
➢ Synthetic zeolite are porous and posses get structure.
➢ They are prepared by heating together china clay, feldspar and soda ash.
➢ such zeolites possess higher exchange capacity per unit weight than natural
zeolites.

10. Zeolite

11. Name Structure Formulae
Analcime NaAlSi2O6·H2O
Chabazite (Ca0.5,Na,K)4[Al4Si8O24]•12H2O
Clinoptilolite (Na,K,Ca)2-3Al3(Al,Si)2Si13O36•12(H2O)
Hulandite (Ca,Na)2-3Al3(Al,Si)2Si13O36·12H2O
Natrolite Na2Al2Si3O10·2H2O
Phillipsite (Na,K,Ca)1-2(Si,Al)8O16•6(H2O)
Stilbite NaCa4(Si27Al9)O72·28(H2O)
Thomsonite NaCa2Al5Si5O20·6H2O
Mordenite (Ca,Na2,K2)Al2Si10O24•7(H2O)
Erionite (Ca,K2,Na2)2[Al4Si14O36]•15(H2O)
Ferrierite (Na,K)2Mg(Si,Al)18O36•9(H2O)
Common Zeolites Mineral
Microporous and
mesoporous materials

12. ➢ Inorganic, crystalline, aluminosilicate materials.
➢ Natural aluminosilicate minerals with crystal three-dimensional structure.
➢ Hydrated cations are located inside framework structure and weakly bound with
structure.
➢ Zeolites have different dimensions of pores and channels responsible for their
physical and chemical properties.
➢ Chemically and thermally stable.
➢ Zeolite Formed from weathering, dissolution and reprecipitation in fine grained high
silica igneous rocks or sedimentary deposits derived from them- Generally looking
for tuffs or glassy volcanic flows.
➢ Zeolites transform to other minerals under weathering, hydrothermal alteration or
metamorphic conditions
➢ Advantages of these natural minerals are their large deposits on the Earth,
easiness of exploitation and mostly unnecessary treatment for practical application.
➢ Difference between natural zeolite minerals is manifested in content of hydrated
cations which occupied pores and channels, ratio of Si/Al in structure and number
of water molecules
➢ ~50 different minerals of zeolites are discovered in nature, but some of them have
commercial valuable. Many natural zeolites are synthesized in laboratory.
Deposits and properties
NATURAL ZEOLITES
12

13. Zeolite facts
 They are found in geologically young volcanic fields
 Zeolites are a group of silicate minerals with unusual properties with industrial
importance.
 Tektosilicates, networks of SiO4 tetrahedrons with some Al substituting for Si
 Strong bonds support framework
 Hydrated aluminosilicates with particularly open frameworks of (Si,Al)O4
tetrahedrons
 Open cavities contain cations (Ca, K, Na, Ba)
 Cations balance negative charge of framework
 Ions are easily exchanged, move freely through framework
 Remain stable after losing water from structure
 Heating causes water loss at a continuous rate
 Form by chemical reaction between volcanic glass and saline water
 They usually form beautiful well-formed crystals with pale colors, and are
relatively soft and can be crushed and powdered.

14. Zeolite structure
The primary building unit of zeolites are cations coordinated
tetrahedrally by oxygen. These tetrahedra are connected via corners,
thus forming the crystal structure of the specific zeolite.
www.mpi-muelheim.mpg.de/. ../zeolites_c2.html

15. Properties of Zeolites
• All commercially useful zeolites owe their
value to one or more of three properties:
adsorption, ion exchange, and catalysis
www.mpi-muelheim.mpg.de/. ../zeolites_c2.html

16. Zeolite stability fields
All zeolites are formed in aqueous solution. The water molecules act as
“templates”, which are necessary in order to form a porous structure.
Most zeolites are formed from basic solution (exceptions are fluoride
syntheses) which favours four coordinated aluminium.
Zeolites are formed in the low temperature end of the hydrothermal
synthesis (70- 300oC) due to the open structure and high water content.
Higher temperatures often gives denser materials.
16

17. What special properties do zeolites have?
Zeolites are very stable solids that resist the kinds of environmental conditions that
challenge many other materials. High temperatures don't bother them because they
have relatively high melting points (over 1000°C), and they don't burn. They also resist
high pressures, don't dissolve in water or other inorganic solvents, and don't oxidize in
the air. They're not believed to cause health problems through, for example, skin
contact or inhalation, though in fibrous form, they may have carcinogenic (cancer-
causing) effects. Since they're unreactive and based on naturally occurring minerals,
they're not believed to have any harmful environmental impacts. Although zeolites
might sound incredibly boring, their stable and unreactive nature isn't what makes them
useful.
The most interesting thing about zeolites is their open, cage-like, "framework" structure
and the way it can trap other molecules inside it. This is how water molecules and alkali
or alkaline-Earth metal ions (positively charged atoms with too few electrons,
sometimes called cations) become a part of zeolite crystals-although they don't
necessarily remain there permanently. Zeolites can exchange other positively charged
ions for the metal ions originally trapped inside them (technically this is known as cation
exchange) and, as Cronstedt found over 250 years ago, they can gain or lose their water
molecules very easily too (this is called reversible dehydration).
Zeolites have regular openings in them of fixed size, which let small molecules pass
straight through but trap larger ones; that's why they're sometimes referred to as
molecular sieves. Unlike natural zeolites, which occur in random forms and mixed sizes,
synthetic zeolites are manufactured in very precise and uniform sizes (typically from
about 1μm to 1mm) to suit a particular application; in other words, they're made a
certain size to trap molecules of a certain (smaller) size inside them.
Although all zeolites are aluminosilicates, some contain more alumina, while others
contain more silica. Alumina-rich zeolites are attracted to polar molecules such as water,
while silica-rich zeolites work better with nonpolar molecules.
17

18. Physical characteristics of some naturally occurring zeolites
18

19. Nanoporous Materials
 Nanoporous materials consist of a regular organic or inorganic
framework supporting a regular, porous structure.
 Pores are by definition roughly in the nanometre range, that is
between 1x10-7 and 0.2x10-9 m.
 Nanoporous materials can be subdivided into 3 categories, set out
by IUPAC:
➢Microporous materials: Such as Zeolites, 0.2–2nm
➢Mesoporous materials: 2–50 nm
➢Macroporous materials: 50–1000 nm
19

20. Mining
Both bedded sedimentary and thick volcanoclastic zeolite deposits are
mined by surface methods.
Conventional earth-moving equipment, including scrapers and loaders,
are used to mine the zeolite bed. Selective mining and blending during
removal or stockpiling controls any variation in the purity of the ores.
Sampling drill holes, the area being mined, the haulage truck, and the
process stream are all used for quality control.
20

21. Formation of Zeolites
Formed by alteration reactions
Temperatures range from 27°C - 55°C
pH is typically between 9 and 10
Nature requires 50 - 50,000 years to complete the reaction
Mostly altered volcanic glasses
Fine-grained volcanic ashes or pumice particles are especially
susceptible to alteration
Starting materials can also be minerals, like nepheline, leucite,
and feldspars
Alteration in different environments: hydrothermal, saline or
alkaline lakes, and groundwater
The alteration conditions of these three environments are
completely different with respect to chemistry, concentration,
and pH of the reacting solution, solid/liquid ratio, temperature,
reaction in closed or open system.

22. Zeolite Process
➢ For softening of water by zeolite process, hard water is percolated at a
specified rate through a bed of zeolite, kept in a cylinder.
➢ The hardness causing ions(Ca2+ ,Mg2+ ,etc.) are retained by the zeolite as
CaZe and MgZe ; while the outgoing water contains sodium salts.
Reactions
Na2Ze + Ca(HCO3)2  CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2  MgZe + 2NaHCO3
(Zeolite) (Hardness)
Na2Ze + CaCl2 (or CaSO4)  CaZe + 2NaCl
(or Na2SO4)
Na2Ze + MgCl2 (or MgSO4)  MgZe +
2NaCl(or Na2SO4)
(Zeolite) (Hardness)

23. Regeneration
➢ After some time, the zeolite is completely is completely converted into calcium
and magnesium zeolite and it ceases to soften water, i.e., it gets exhausted.
➢ At this stage, the supply of hard water is stopped and the exhausted zeolite is
reclaimed by treating the bed with a concentrated (10%) brine (NaCl) solution.
CaZe (or MgZe) + 2Nacl  Na2Ze + Cacl2 (or MgCl2)
(Exhausted zeolite) (Brine) (Reclaimed (Washings)
zeolite)
➢ The washing (containing Cacl2 and MgCl2 ) are led to drain and the
regenerated zeolite bed thus-obtained is used again for softening
purpose.

24. Limitations of process:
1. If the supply of water is turbid, the suspended matter must be removed (by
coagulation, filtration, etc.), before the water is admitted to the zeolite bed ;
otherwise the turbidity will clog the pores of zeolite bed, thereby making it
inactive.
2. If water contains large quantities of coloured ions such as Mn2+ and Fe2+,they
must be removed first, because these ions produce maganese and iron zeolite,
which cannot be easily regenerated.
3. Mineral acids, if present in water, destroy the zeolite bed and,therefore, they
must be neutralised with soda, before admitting the water to the zeolite
softening plant.

25. Lighter color is the altered volcanic ash with
clinoptilolite at the St. Cloud zeolite mine
Source= http://www.ees.nmt.edu/~ranck/zeolite.html

26. St. Cloud Zeolite Mine
The Cuchillo Negro clinoptilolite deposit mined by the St.
Cloud campany is shown here.

27. Advantages and Disadvantages of process
Advantages of process
1. It removes the hardness almost
completely and water of about 10 ppm
hardness is produced.
2. The equipment used is compact,
occupying a small space.
3. No impurities are precipitated, so there
is no danger of sludge formation in the
treated water at a later stage.
4. The process automatically adjust itself
for variation in hardness of incoming
water.
5. It is quite clean.
6. It requires less time for softening.
7. It requires less skill for maintenance as
well as operation.
Disadvantages of process
1. The treated-water contains more sodium
more sodium salts than in lime-soda process.
2. The method only replaces Ca2+ and Mg2+ ions,
but leaves all the acidic ions ( like HCO3
- and
CO3
2-) as such in the softened water. When
such softened water (containing NaHCO3 ,
Na2CO3 ,etc.) is used in boilers for steam
generation, sodium bicarbonate decomposes
producing CO2 , which causes corrosion ;and
sodium carbonate hydrolysis to sodium
hydroxide, which causes caustic
embrittlement.
3. High turbidity water cannot be treated
efficiently by this method, because fine
impurities get deposited on the zeolite bed,
there by reacting problem for its working.

28. What are zeolites used for?
Natural and synthetic zeolites are used commercially because of their unique
adsorption, ion-exchange, molecular sieve, and catalytic properties.
Major markets for natural zeolites (About 80% of Zeolite Use) are:
➢Animal Feed
➢Pet Liter
➢wastewater treatment
➢Water Purification
➢Odor Control
Other Uses:
➢Fungacide or pesticide carrier
➢Oil absorbent / Desiccant
➢Catalyst
➢Horticulture applications (soil conditioners and growth media)
➢Aquaculture (keeps water clean in the presence of overpopulation)
Major use categories for synthetic zeolites are
➢catalysts,
➢detergents,
➢molecular sieves.
28

29. Uses of Zeolites
Source: www.egam.tugraz.at/ app_min/sci_topics/zeolithe/

30. Uses of Zeolite

31. USESOFZEOLITES AS MOLECULAR SIEVES
- Used as molecular sieves where they can retain molecules that can fit into their
molecular cavities.
- Is to separate straight-chain hydrocarbons from branched-chain hydrocarbons in gas
chromatography.
AS ION EXCHANGERS
- Used in exchange (ions) columns where the ions in zeolites can be exchanged with other ions.
-This process needs Soften Hard Water. When hard water containing Ca2+ and Mg2+ ions will
pass through zeolite, then the Ca2+ and Mg2+ ions will be replaced with Na2+ ions
Na2Z + Ca2+ (aq) <--> CaZ + 2Na+
AS CATAYLST
- Have the ability to act as catalyst for chemical reactions which
take place within internal cavities.
- Used in many organic reactions

32. Application Of Natural Zeolites
Zeolites are microporous, aluminosilicate Tectosilicates minerals commonly used as commercial
adsorbents and catalysts.
A major application of the zeolites in catalysis: Zeolite is in acid catalyzed reactions such as
alkylation, acylation, electrophilic aromatic substitution, cyclization, isomerization and condensation.
Actually a family of related mineral structures with very high internal surface area:
➢ It can act as a molecular sieve by grabbing some small molecules while letting larger ones pass
High surface area provides a big surface area to stage reactions – makes a great catalyst.
Zeolites have relatively large CEC and are useful for a variety of environmental remediation
processes.
 APPLICATION of natural zeolites is based on or more of the following properties:
➢ Cation Exchange
➢ Ion-exchangers
➢ Adsorption And Related Molecular Sieving
➢ Water Softeners
➢ Dehydration And Rehydration
➢ Biological Activity
➢ Excellent Catalysts /catalytic
32

33.  the ability to exchange inherent cations for other cations on a basis of ion
selectivity
 high cation exchange capacity for heavy metal cations that can be removed
from liquid effluents through the process of ion-exchange. These cations
include lead, silver, cadmium, cobalt, zinc, copper, mercury, magnesium,
iron, aluminium, chromium and others. Some natural zeolites are applicable
in industries such as mining, electroplating and electronics. Giant industrial
houses, like IBM, have deployed this application for treatment of
wastewater containing heavy metals.
 selectivity for ammonium cations, the natural zeolites lower the level of
ammonium in wastewaters and sewages to non-toxic, acceptable levels.
The zeolite beds can be regenerated and recycled indefinitely.
33
Cation exchange
33

34. Adsorption and related molecular sieving
 The adsorption process is fully reversible and of purely physical nature. The
structure of the zeolite is unchanged during the adsorption process and its later
regeneration.
 The adsorption on molecular sieves is therefore dependent on the following
physical molecular properties:
➢ Size and Shape; molecules or ions larger than the pore opening of the
zeolite can not be adsorbed, smaller molecules or ions can.
➢ Molecular Polarity; due the charge on outer and inner zeolitic surface
particle, molecules with large polarity or polarizability can be adsorbed
preferentially under identical conditions.
➢ this property is used for selective absorption of organic molecules and for
absorption of radioactive ions (absorber of Sr and Cs radioisotopes in the
nuclear industry and for clean up of nuclear accidents - applied in the Chernobyl
disaster).
➢ adsorption process on zeolite is used to remove polar H2O, H2S, and CO2 from
natural gas and developed a zeolite-adsorption process for purifying methane
produced in a landfill.

35. ➢Adsorption in zeolites is significantly different from adsorption in e.g.
silica gel or active coal, which have a broad size distribution of pore
sizes, and where the size of the pores are in the range of 10 nm.
➢In zeolites the porosity is determined by the crystalline structure, i.e. the
pores are arrnged in a regular fashion with only one (or a few) discrete
pore sizes. Also the pores have molecular dimensions.
➢The implication of this is the use of zeolites as adsorbants and molecular
sieves.
➢Mainly used for water adsorption (very low equilibrium water vapour
pressure) Gas (hydrogen?) storage materials
➢Molecular sieving effect due to size limitation imposed by framework
structure and cation size and position.
➢Also weaker interactions:
➢N2-O2 separation
35
Adsorption Ion exchange Catalytic activity

36. Dehydration and rehydration
 Natural zeolites may hold water up to 60% of their weight due to a high
porosity of the crystalline structure. Water molecules in the pores could be
easily evaporated or reabsorbed without damage to such structures.
 Zeolites assure a permanent water reservoir, providing prolonged moisture
during dry periods; they also promote a rapid rewetting and improve the lateral
spread of water into the root zone during irrigation. This results in a saving in
the quantity of water needed for irrigation.
36

37. Biological activity
Natural zeolite has been shown to exhibit diverse
biological activities and has been used successfully for the
treatment in medical therapy
Promotes better plant growth by improving the value of
fertilizer, helps preventing the plant from burning, that can
be caused by over use of fertilizer, by trapping and slowly
releasing valuable nutrients
as Additive in concentrated animal growing facilities
improve feed conversion, reduce airborne ammonia up to
80%, act as a mycotoxin binder, and improve bone
density, it can be used in general odour elimination for all
animal odours

38.  Modifying the surface of clinoptilolite with long-chain quaternary amines
allowed it to adsorb benzene, toluene, and xylene in the presence of water
 Surface modified natural zeolites remove toxic compounds from animal food
 Natural zeolite can be treated further with additional amine to produce
anion exchangers capable of taking up chromate, arsenate, selenate, and
other metal oxyanions from aqueous solutions
Surface modification of natural zeolites
38

39. Water Adsorption/Desorption
• Adsorbing and desorbing water without damage to the crystal structure, make excellent
desiccants
• Low cost, efficient media for heat storage (to include storage of waste and/or off-
peak heat energy like solar systems) and solar refrigeration applications.
Gas Adsorption
 Zeolites adsorb many gases on a selective basis
 Specific channel size (2.5 to 4.3A) enables zeolites to act as molecular gas sieves
 Selectively adsorb ammonia, hydrogen sulfide, carbon monoxide, carbon dioxide,
sulfur dioxide, water vapor, oxygen, nitrogen, formaldehyde, and others.
 Public toilets, horse stables, chicken houses, and feed lots, pet litter trays release
ammonia fumes
 Adding zeolites can minimize odors
Zeolite Applications:
Water Treatment uses include water softening, remove metals (Cu+2, Pb+2, Zn+2), and
radioactive waste treatment (Sr90, Ce137), and wastewater treatment (sequester pollutants)
Remove ammonia in aquaculture tanks
In agriculture, control high nitrogen levels and reduce pollution caused by field runoff.
Ion Exchange

40. Zeolite Sources
The most important deposits are in the United States,
Mexico, Ukraine, Slovakia, Italy, Greece, Turkey,
Russia, Serbia, Romania, Bulgaria, Georgia, Armenia,
Cuba and Croatia.
Antigua, Argentina©, Australia©, New South Wales,
Bulgaria, Canada (Nova Scotia, British Columbia), Chile,
China©, Czechoslovakia ©, France, Germany©, Hungary©,
Iceland, Indonesia©, Italy©, Japan©, Korea©, Mexico©,
New Zealand, Poland, S. Africa©, Romania©, Spain©, UK,
USSR©, Yugoslavia©.
Currently, the world’s annual production of natural
zeolite is ~4 million tons.
(The © means commercial development)

41. World Resources
World Zeolites Production to Reach 2.98 Mln Tonnes in 2017
World resources have not been estimated for natural zeolites.
An estimated 120 million tons of chabazite, clinoptilolite, erionite, mordenite, and phillipsite is present
in near-surface deposits in the Basin and Range province in the United States.
Countries that mine large tonnages of zeolites typically use them in low-value, high-volume
construction applications, such as dimension stone, lightweight aggregate, and pozzolanic cement.
As a result, production data for some countries do not accurately indicate the quantities of natural
zeolites used in the high-value applications that are reflected in the domestic production data. World
reserves of natural zeolites have not been estimated.
Deposits occur in many countries, but companies rarely, if ever, publish reserves data.
Further complicating estimates of reserves is the fact that much of the reported world production
includes altered volcanic tuffs with low to moderate concentrations of zeolites that are typically used in
high-volume construction applications. Some deposits should, therefore, be excluded from reserves
estimates because it is the rock itself and not its zeolite content that makes the deposit valuable.
Mine production Reserves
2009 2010 2015 2016
World
reserves are
not
determined
but are
estimated to
be large
China 2,000,000 2,000,000 2,000,000 2,000,000
Japan 155000 150000
Korea, Republic of South 165000 21000 205,000 205,000
United States 59500 59000 75,100 80,000
Turkey 100000 100000 70,000 60,000
SLOVAKIA 90000 85000
New Zealand 65,000 80,000
Cuba 43,000 51,000
Jordan 425000 140000 13,000 12,000
Other countries 5500 5000 350,000 350,000
World total (rounded) 3000000 2750000 2,800,000 2,800,000

43. World Consumption of Zeolites - 2016
Source IHS

44. Markets Opportunities for Natural Zeolite Producers Worldwide
➢Zeolite-based Lightweight Cements for the Oil and Gas Industry
➢Zeolite-based Lightweight, High-strength Cement and Concrete for
Building Materials
➢Specialty Sorbents, Cation Exchangers and Catalysts
➢Municipal and Potable Water Treatment
➢Industrial, Mine, Sewage and Oil Field Effluent Treatment Packaging
for Fruits and Vegetables
➢Antimicrobial Agents
➢Industrial Wastewater Treatment
➢Air Purification
➢Passive Minewater Treatment – AMD, Heavy metals, trace organics
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45. Which Zeolites have commercial value?
Chabazite and clinoptilolite are the 2 out of the 48
minerals in the zeolite group which have the most
commercial applications.
Occur in Cenozoic age tuffaceous sediments principally in
the Western US.
Chabazite and Clinoptilolite formed over a long period of
time are the end product of the chemical reaction between
volcanic ash glass shards and alkaline water.
Because of their high silica to alumina ratios ranging from
2:1 for chabazite to 5:1 for clinoptilolite, these minerals are
stable and less likely to dealuminate in acidic solutions than
are synthetic zeolites.

46. St. Cloud Zeolite Plant
St. Cloud Mining Company has emerged as the largest
producer of natural zeolite in North America. The zeolite
mineral, clinoptilolite, is an absorbent volcanic ash with
unique physical, chemical, and cation exchange properties
used in agriculture, industrial and environmental
applications.
Source=http://www.stcloudmining.com/

47. Mining St. Cloud Zeolite
St. Cloud’s zeolite deposit contains an estimated 18.3 million tons of
clinoptilolite resources and the production facility has a capacity in
excess of 100,000 tons per annum. The operation includes facilities for
custom sizing, bagging, blending and manufacturing of added value
products. St. Cloud sells zeolite primarily through a network of
brokers, distributors and manufacturers.
Source=http://www.stcloudmining.com/

48. Zeolite Markets
Relatively new, since1960s
Most consumed within country produced
Diverse markets
Steady growth is anticipated for the rest of the
1990s for agricultural, industrial, and consumer
applications. The strongest areas of market growth
in North America are expected to be in sewage
treatment, deodorants, pet litter, soil treatment,
and nuclear waste treatment and containment.

49. Value of Zeolites
Usually determined by cost of processing and
added value
Mining costs $3-6/Ton
Processed $30-120/Ton
Pet litter, fish tank, deodorant $.50-4.50 kg
Special apps = $1000s /ton (radioactive waste
filter media or catalysts in petroleum refining,
……….etc)

50. Transporting Zeolites
Generally transported by highway or rail
carriers in bulk, in one–ton super–sacks or in
multi–wall paper bags, usually palletized.
Do not require special handling
Costs affected by distance must transport
Specialty zeolites worth shipping farther

51. Alternates
Synthetic zeolites (customized molecular sieves) are the
major alternate materials to natural zeolites.
Synthetic zeolites can tailor physical and chemical
characteristics to serve many applications more closely and
they are more uniform in quality than their natural
equivalents.
Natural zeolites advantage over synthetic materials: Ce and
Sr adsorption in radioactive waste cleanup, able to function
at lower pH levels, much lower in cost than synthetic zeolite
products.
Activated carbon, silica gel, & similar materials are more
effective than zeolites for many ion–exchange applications
and are not disproportionately more expensive.
Bentonite, attapulgite, and others show selective high
absorbency, available in a competitive price range.

52. Problems with Zeolites
The synthetic zeolites pose no problems, readily
made from abundant raw materials, present no
toxic or environmental problems.
Naturally occurring zeolites are excluded from
many important commercial applications where
uniformity and purity are essential
Natural zeolites must penetrate markets where
other materials are already used and accepted
Natural zeolites were over-marketed in the 70’s,
created stigma, must now overcome
Some zeolites are fibrous, all are silicates
No industrial standards exist for natural zeolites,
harder to market, need ASTM or other standards
published

53. Future of Zeolites
A healthy, growing industry with continued expansion into new
applications and steady demand in industrial markets
Most of the activity and growth has been in the synthetic zeolite
field.
Natural zeolite market likely to continue on a slow and steady
basis.
Natural zeolites domestic market for catalysis and petroleum
refining, nuclear waste treatment, and odor control, pollution
control, and energy cost and efficiency issues will continue and
expand.
Higher energy costs and greater environmental demands will spur
zeolite production and sales significantly.
For the next decade, natural zeolites should emerge as a better–
defined mineral commodity, and North America will become a
leading producer.

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