Geologi Mineral Industri

Geology and Industrial Applications

of Zeolite

Dr.rer.nat. I Wayan Warmada

Laboratory of Geochemistry & Laboratory Mineral Resources
Department of Geological Engineering FT-UGM
E-mail: warmada@ugm.ac.id

Yogyakarta, 21 Oktober 2021

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Terminology of zeolite

The name ’zeolite’ was introduced by the Swedish mineralogist

Cronstedt in 1756 for certain silicate mineral in allusion to their
behaviour on heating in a borax bread (Greek zeo = boil; lithos =
stone).
Definition: a zeolite mineral is a crystalline substance with a
structure chracterized by a framework of linked tetrahedra, each
consisting of four O atoms surrounding a cation.
I This framework contains open cavities in the form of channels and
cages. These are usually occupied by H2 O molecules and
extra-framework cations that are commonly exchangeable.
I The channels are large enough to allow the passage of guest
species. In the hydrated phases, dehydration occurs at
temperatures mostly below about 400 °C and is largely reversible.
I The framework may be interrupted by (OH,F) groups; these occupy
a tetrahedron apex that is not shared with adjacent tetrahedra.

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Terminology of zeolite

Construction of zeolite frameworks (Pálinkó et al., 2013).

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Zeolite properties

According to Breck (1974), the important physical and chemical

properties of zeolite are:
I High degree of hydration
I Low density and large void volume when dehydrated
I Stability of the crystal structure of many zeolites when dehydrated
I Cation exchange properties
I Uniform molecular-sized channels in the dehydrated crystals
I Ability to adsorb gases and vapors
I Catalytic properties
Molecular sieves are materials that can selectively adsorb
molecules on the basis of their size, shape, or electrical charge
(Clifton, 1987).
Commercial applications of zeolites are based on the following
properties: molecular sieving, ion exchange, adsorption, and
catalysis.

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Zeolite classifications

Type Typical Unit-Cell Formula Crystal System Void Volume, %

Analcime Na16 (Al16 Si32 O96 )·16H2 O Cubic 18
Chabazite (Na2 Ca)6 (Al12 Si24 O72 )·40H2 O Hexagonal 47
Clinoptilolite (Na4 K4 )(Al8 Si40 O96 )·24H2 O Monoclinic 39
Erionite (Na2 Ca6 K)9 (Al9 Si27 O27 )·27H2 O Hexagonal 35
Ferrierite (Na16 (Al16 Si32 O96 )·16H2 O Orthorhombic 0
Heulandite Ca4 (Al8 Si28 O72 )·24H2 O Monoclinic 39
Laumontite Ca4 (Al8 Si16 O48 )·16H2 O Monoclinic 34
Mordenite Na8 (Al8 Si40 O96 )·24H2 O Orthorhombic 28
Phillipsite (Na2 K)10 (Al10 Si22 O62 )·20H2 O Orthorhombic 31
Linde A∗ Na12 (Al12 Si12 O48 )·27H2 O Cubic 47
Linde B∗ Na66 (Al66 Si106 O364 )·264H2 O Cubic 50

∗) Linde A and Linde X are synthetic phases. Source: Kogel et al. (2006)

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Zeolite classifications

Type Specific Gravity Channel Dimensions Thermal Stability IEC∗∗

Analcime 2.24 – 2.29 2.6 High 4.54
Chabazite 2.05 – 2.10 3.7 × 4.2 High 3.81
Clinoptilolite 2.16 3.9 × 5.4 High 2.54
Erionite 2.02 – 2.08 3.6 × 5.2 High 3.12
Ferrierite 2.14 – 2.21 4.3 × 5.5 High 2.33
Heulandite 2.10 – 2.20 4.0 × 5.5 Low 2.91
Laumontite 2.20 – 2.30 4.6 × 6.3 Low 4.25
Mordenite 2.12 – 2.15 2.9 × 5.7 High 2.29
Phillipsite 2.14 – 2.20 4.2 × 4.4 Low 3.87
Linde A∗ 1.99 4.2 High 5.48
Linde B∗ 1.93 7.4 High 4.73

∗∗) IEC, Ion-Exchange Capacity in meq/100g (calculated from unit-cell formula)

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Geology of zeolite
Mineralogy

Zeolites occur in a variety of geologic settings, mostly as alteration

or authigenic minerals, low temperature–low pressure minerals in
metamorphic systems, secondary minerals in weathered zones, or
in veins.
Nine zeolites commonly occur in sedimentary rocks: analcime,
chabazite, clinoptilolite, erionite, ferrierite, heulandite,
laumontite, mordenite, and phillipsite.
Analcime and clinoptilolite are by far the most abundant.
Chabazite, clinoptilolite, erionite, mordenite, and phillipsite are
the only zeolite minerals with commercial applications today.
Erionite, which has been classified as a human carcinogen, has
only limited industrial applications.
These five are the only zeolites that are abundant in nature and
have adequate ion-exchange, absorbency
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Geology of zeolite
Mineralogy

The basic structure of zeolites consists of (AlSi)O4 tetrahedra,

wherein each oxygen is shared by two tetrahedra: thus, the atomic
ratio O:(Si+Al) is 2.
The net negative charge of the structure is balanced by
exchangeable cations, which are loosely held within the central
cavities and surrounded by water molecules.

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Geology of zeolite
Mineralogy

a-d) glass shards (de’Gennaro et al., 2000).

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Geology of zeolite
Mineralogy

a) amorphous gel-like phase; b) initial glass alteration product with fibrous

aspect; c) acicular cluster (Php?); d) Php crystals.

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Geology of zeolite
Mineralogy

e) Php crystals lining cavities in glass shard; f) glass shard; g) euhedral Cbz
crystals; h) acicular cluster covering glass shards structure.

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Geology of zeolite
Mineralogy

a) zeolitized spherulites; b) Cpt crystal on glass shard; c) Hul crystal coating

bubble walls; d) opal-CT lephispheres on Cpt.

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Geology of zeolite
Mineralogy

e) opal-CD lephisphere encrusting Cpt; f) encrusting opal-CT; g) fibrous Mor;

h) Adl-like K-feldspar crystals (Cerri et al., 2001).

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Geology of zeolite
Mineralogy

a) cavity filled by Qz; b) subtle Qz vein; c) tardive Qz vein in Pl; d) Anl

crystals (Cerri et al., 2001).

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Geology of zeolite
Mineralogy

e) subtle sedimentary structures; f) Cpt cementing detrital clasts; g) opal-CT

lephispheres along with Cpt crystals; h) Sme aggregates and Cpt crystals

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Geology of zeolite
Origin

Zeolite minerals occur in several geologic settings and can be

formed from a variety of starting vitric or lithic material within an
extended range of physiochemical conditions.
Volcanic glass of acid to intermediate composition is the most
common precursor for zeolite minerals. Less common precursors
include microcrystalline quartz, opal, and feldspars.
Nearly all the minable zeolite deposits in the world occur as
zeolitized ash fall tuffs interbedded with lacustrine sediments,
zeolitized vitroclastic tuffs in volcanic rocks, and zeolitized
vitrophyres and vitroclastic tuffs as a result of hydrothermal
alteration.
Pressure, temperature, and time are three important factors that
produce zeolite alteration of the vitric precursor.

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Geology of zeolite
Origin

The composition of the vitric component and the composition of

the reactive pore water that contains cations such as H+ , Na+ ,
Ca2+ , K+ , and H4 SiO4 are important factors needed to produce
zeolitic alteration.
Based on zeolite geologic setting, mineralogy, and genesis,
Sheppard (1973) classified zeolite deposits into the following
types:
I Closed system: deposits formed from volcanic materials in
hydrologically closed, saline/alkaline lake systems. Erionite,
chabazite, and phillipsite chracterize the saline, alkaline-lake
deposits.
I Open system: deposits formed in hydrologically open, freshwater
lake or groundwater systems. Clinoptilolite and mordenite are the
principal zeolites of open system deposits.
I Burial metamorphic: ...

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Geology of zeolite
Origin

Based on zeolite geologic setting ... (cont’d):

I Burial metamorphic: deposits formed by low-grade, burial
metamorphism (or burial diagenetic deposits). With increase of
depth, the deposits usually contain zone of (1) fresh ash, (2) alkali
clinoptilolite, (3) clinoptilolite–mordenite, (4) analcime, and (5)
albite.
I Hydrothermal or hot spring: deposits formed by hydrothermal or
hot spring activity.
I Deep marine: deposits formed in deep marine environments, i.e.,
clinoptilolite and phillipsite. Marine zeolites form at low
temperatures and may replace as much as 80% of the marine
sediments.
I Weathered zone: deposits formed in soils, most commonly from
volcanic materials. Analcime has been reported in alkaline, saline
soils in the eastern San Joaquin Valley, California.

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Characterizations
Methods

Natural zeolite minerals are identified primarily by their crystal

habit.
The principal methods of zeolite identification are X-ray
diffraction and scanning electron microscopy. Neither optical
microscopy nor differential thermal analysis is particularly useful
for identifying zeolite minerals.
I X-ray Diffraction (XRD)
I Scanning Electron Microscopy (SEM)
I Optical Microscopy
I Different Thermal Analysis (DTA)

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Characterizations
Methods

In characterizing zeolitic materials for commercial uses, it is

important to quantify other physical and chemical properties
required by the specific application.
The following are physical and chemical properties and tests that
may typically be required:
I wet chemical analysis;
I CEC;
I specific gravity and bulk density;
I brightness, whiteness, and color;
I hydration/dehydration;
I gas adsorption;
I attrition in water;
I internal and external surface are;
I pore size;
I and volume.

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Zeolite characteristics

A) analcime (Anl); B) chabazite (Cbz); C) heulandite (Hul); D) laumontite

(Lmt)

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Zeolite characteristics

A) zeolite outcrop (Serut); B) Sidomulyo; C–D) zeolite hand specimen from

Sidomulyo

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Zeolite characteristics

A–B) Cbz in thin section, PPL and XPL; C) Hul, XPL; D) Lmt, XPL.

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Zeolite characteristics

A) Mor crystals, in SEM; B) Cpt; C–D) Mor and Cpt. All sample from
Sidomulyo.

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Zeolite characteristics

1–2) Cbz; 3) Php; 4) Hul (Passaglia & Vezzalini, 1985).

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Zeolite characteristics

a) acicular crystals of Php; b) rhombohedral Cbz; c) Php–Cbz; d) Anl

(de’Gennaro et al., 2000)

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Zeolite applications
The principal uses of zeolites at this time are:
I Amoniumion removal from sewage and industrial effluents,
aquarium, and commercial fish farms
I Odor control in animal absorbents, floor and carpet cleaning
products, and industrial floor absorbents
I Removal of heavy metal ions from nuclear, mine, and industrial
effluents
I Agricultural applications as soil conditioners and animal feed
supplements
I Desiccants used to adsorb water vapor in sealed containers and
packaging
I Carriers for bacteria and enzymes
I Gas separation
I Catalysis
Agricultural products: zeolites are used as soil conditioners and
fertilizer extenders, particularly in Japan, Cuba and Eastern
Europe.

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Zeolite applications

Animal nutrition: adding clinoptilolite to animal feed in controlled

amounts increase utilization of feed and decrease ammonia stress
in animal digestive system.
Aquaculture: zeolite are used in aquarium, fish farms, and fish
hatcheries to avoid the buildup of ammonia to toxic levels.
Catalysis and petroleum refining: zeolite with large channel sizes
have large internal surface areas and can catalyze many type of
reactions.
Desiccants: activated chabazite is used as a carrier and desiccant in
packaged enzymes and bacteria used to inoculate silage. Partially
activated clinoptilolite and chabazite are used as anticacking
agents in cattle feeds containing mineral and organic supplements.

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Zeolite applications

Dimension stone: zeolitic tuffs have been used for thousand of

years as lightweight, durable dimension stone. Zeolitic tuffs have
low bulk densities, are weather resistant, have superior insulating
properties, and can be easily cut into attractive stone.
Gas separation: zeolites are used to separate nitrogen and oxygen
to produce a gas stream containing up to 95 % oxygen. Mordenite
appears to be the best natural zeolite for oxygen generation,
although clinoptilolite and chabazite have also been used.
Ion-exchange applications: the ability of exchange cations is one of
the most important properties of zeolites. Cation-exchange capacity
is a measure of the number of cations per unit weight available for
exchange.

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Zeolite applications

Paper fillers: clinoptilolite, have been used as fillers in some special

paper products.
Pozzolan and cement: pozzolan is a naturally occuring
cementaceous material that can replace up to 25 % of the portland
cement in concrete. Zeolitic tuff have been used as pozzolan in
many places in the world.
Sewage treatment: clinoptilolite and chabazite remove ammonia
and some heavy metals from sewage and other effluent streams.
Solar energy and heat exchange: chabazite and clinoptilolite absorb
and release heat from solar radiation for air conditioning,
refrigeration, and water heating applications.

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Zeolite applications

Stack gas cleanup: natural zeolites can be used to remove sulfur

dioxide from stack gases of coal-burning power plants.
Clinoptilolite and mordenite can adsorb as much as 200 mg of SO2
per gram of zeolite under static conditions and as much as 40 mg
under dynamic conditions.

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)

Central Java and Yogyakarta

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)

Central Java and Yogyakarta

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)
3 Geger Bitung, Cisolok, and Cikembar (Sukabumi)

Central Java and Yogyakarta

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)
3 Geger Bitung, Cisolok, and Cikembar (Sukabumi)
4 Cikalong (Tasikmalaya)

Central Java and Yogyakarta

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)
3 Geger Bitung, Cisolok, and Cikembar (Sukabumi)
4 Cikalong (Tasikmalaya)

Central Java and Yogyakarta

1 Wadaslintang (Wonosobo)

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)
3 Geger Bitung, Cisolok, and Cikembar (Sukabumi)
4 Cikalong (Tasikmalaya)

Central Java and Yogyakarta

1 Wadaslintang (Wonosobo)
2 Nanggulan (Kulonprogo)

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)
3 Geger Bitung, Cisolok, and Cikembar (Sukabumi)
4 Cikalong (Tasikmalaya)

Central Java and Yogyakarta

1 Wadaslintang (Wonosobo)
2 Nanggulan (Kulonprogo)
3 Serut, Sampang, Hargomulyo, Gedangsari, and Sidomulyo
(Gunung Kidul)

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Occurrences
Java Island

West Java
1 Nanggung (Bogor)
2 Bayah and Leuwidamar (Lebak)
3 Geger Bitung, Cisolok, and Cikembar (Sukabumi)
4 Cikalong (Tasikmalaya)

Central Java and Yogyakarta

1 Wadaslintang (Wonosobo)
2 Nanggulan (Kulonprogo)
3 Serut, Sampang, Hargomulyo, Gedangsari, and Sidomulyo
(Gunung Kidul)
4 Trembono (Klaten)

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Occurrences
Java Island

East Java
1 G. Cagak, Wonosidi (Pacitan)

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Occurrences
Java Island

East Java
1 G. Cagak, Wonosidi (Pacitan)
2 Slahung (Ponorogo)

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Occurrences
Java Island

East Java
1 G. Cagak, Wonosidi (Pacitan)
2 Slahung (Ponorogo)
3 Kali Tengah (Blitar)

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Occurrences
Java Island

East Java
1 G. Cagak, Wonosidi (Pacitan)
2 Slahung (Ponorogo)
3 Kali Tengah (Blitar)
4 Tembarejo and Sumbermajing (Malang)

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References1

Cerri, G., Cappelletti, P., Langella, A., de’Gennaro, M. (2001)

Zeolitization of Oligo-Miocene volcaniclastic rocks from Logudoro
(northern Sardinia, Italy). Contrib Mineral Petrol, v. 140, pp.
404–421.
Graham, I.T., Pogson, R.E., Colchester, D.M., Baines, A. (2003)
Zeolite crystal habits, compositions, and paragenesis; Blackhead Quarry,
Dunedin, New Zealand. Mineralogical Magazine, v. 67, pp. 625–637.
Kogel, J.E., Trivedi, N.C., Barker, J.M., Krukowski, S.T. (eds) (2006)
Industrial Minerals & Rocks, 7th Edition, SME, Inc., Colorado.
Pálinkó, E., Kónya, Z., Kukovecz, A., Kiricsi, I. (2013) Zeolites. In
Vajtai, R. (Ed.) Springer Handbook of Nanomaterials. DOI
10.1007/978-3-642-20595-8_22, p. 819–857.

1 This slide was created by using L X and LAT X 2

Y E ε
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