Zeolites and their Applications

Helen M. Lang
West Virginia University

Zeolite Mineralogy
gy
Zeolites are framework silicates, with a completely linked
framework of tetrahedra
tetrahedra, each consisting of 4 O2surrounding a cation (usually Si4+ or Al3+)
The framework contains open cavities in the form of
channels and cages
Channels and cages are occupied by H2O molecules and
extra-framework
extra
framework cations (K+, Na+, Ca+ and others) that are
commonly exchangeable
Channels are large enough to allow passage of guest
species
In the hydrated phases, dehydration occurs at
temperatures mostly below 400oC and is largely reversible
(Gunter, 2001)

Lower hardness and density than

other
h fframeworkk silicates
ili

Mineral
Quartz
Feldspars
Feldspathoids
Zeolites

H
7
6
5-6
3.5-5.5

G
.
2 65
2.65
2.54-2.75
2.15-2.5
2.0-2.4

Boiling
Boiling stone
stone
Many zeolites fuse readily with marked
intumescence (a swelling up which results
when water is expelled during heating)
Zeolite comes from two Greek words
meaning to boil and stone

Zeolites common properties

Zeolites
High degree of hydration
Low density and large void volume when
hydrated
y
Stability of the crystal structure when dehydrated
Cation exchange properties
Uniform molecular-sized channels in dehydrated
c ysta s
crystals
Ability to absorb gasses and vapors
Catalytic properties
Klein, 2002

Sample Zeolite Formulas

Mineral Name

General Formula

Analcime

Na16[Al16Si32O96]16H2O

Chabazite

(Ca0.5,Na,K)4[Al4Si8O24]12H2O

Clinoptilolite
p

((Na,K)
, )6[[Al6Si30O72]]20H2O

Erionite

K2(Na,Ca0.5)8[Al10Si26O72]28H2O

Heulandite

(Na K)Ca4[Al9Si27O72]]24H
(Na,K)Ca
24H2O

Laumontite

Ca4[Al8Si16O48]18H2O

M li
Mesolite

N 16Ca
Na
C 16[Al48Si72O240]64H
] 64H2O

Scolecite

Ca8[Al16Si24O80]24H2O

Stilbite

NaCa4[Al9Si27O72]30H2O

Some characteristic Cages of Zeolites

From Armbruster & Gunter, 2001, Crystal Structures of Natural Zeolites, RIMG, v. 45

Schematic Representation of Chabazite

Chabazite Movie Jillian Banfield

Molecular Sieve Properties

Schematic illustration of how a zeolite sieve separates

p
a straight-chain
g
hydrocarbon (octane) from a branching-chain hydrocarbon (isooctane).

Structure of Heulandite-Clinoptilolite

Ten-membered and 8membered tetrahedral

rings form channels
parallel to the c-axis
c-axis.
Small green spheres
represent Na, larger light
blue spheres represent
K, small yellow spheres
represent Ca, large blue
spheres represent H2O
molecules.

From Armbruster & Gunter,

2001 C
2001,
Crystal
t l St
Structures
t
off
Natural Zeolites, RIMG, v. 45

(Na,K,Ca0.5)7[Al7Si29O72].22H2O

Two major occurrences of Zeolites

As well-crystallized
well crystallized minerals found in
cavities and veins in basic igneous rocks,
coarse large variety of crystal forms and
coarse,
habits, beautiful crystals
As large deposits of fine
fine-grained
grained zeolites
that are the diagenetic alteration products
of volcanic tuffs and volcanic glass
glass,
recently discovered in western U.S., Cuba,
Turkey Tanzania and elsewhere
Turkey,

Zeolite Crystals

Heulandite - (Ca,Na)2-3Al3(Al,Si)2Si13O3612H2O
from Idaho

Zeolite Crystals

Scolecite
CaAl2Si3O103H
3H2O

Scolecite on Stilbite
CaAl2Si3O103H2O NaCa4[Al9Si27O72]30H2O

Mesolite Na2Ca2Al6Si9O308H2O

Zeolite Crystals

Analcime - Na16[Al16Si32O96]16H2O
Isometric, trapezohedron form common

Zeolite Crystals

Stilbite (Isle of Skye)

Laumontite (India)

Pretty minerals associated with zeolites

Apophyllite KCa4(Si4O10)2F-8H2O is a
sheet silicate commonly assoc. with zeolites

Cavansite Ca(VO)(Si4O10)-4H2O is a
sheet silicate commonly assoc. with zeolites

Properties of Zeolites

Table from Mumpton, 1999, La roca magica

CEC smectite clays

0.8 to 1.5 meq/g

Uses of Zeolites
Ammonium ion removal in waste stream
treatment, sewage treatment, pet litter and
aquaculture
Odor control
Heavy
H
metal
t l iion removall ffrom nuclear,
l
mine, and industrial wastes
Agricultural use, such as soil conditioner
and animal feed supplement
Klein, 2002

Uses of Zeolites
See La roca magica: Uses of natural
zeolites in agriculture and industry
FREDERICK A
A. MUMPTON
Proc. Natl. Acad. Sci. USA
Vol. 96, pp. 34633470, March 1999
Colloquium Paper

Construction Applications
Dimension stone altered tuff has for
millennia been cut into blocks and used as
g stone ((low density,
y high
g p
porosity,
y
a building
homogeneity, low cost)
Pozzolanic cement ((pozzolan, pozzolanic =
a siliceous-aluminous material that will, in finely
divided form and in the presence of moisture,
react with CaOH to form a cement (Webster))

Popped into low density pellets for use in

light-weight aggregates
Mumpton 1999

Dimension Stone

Castel Nuovo (Naples, Italy) constructed of tuffo giallo napolitano (Mumpton 1999)
[the Neapolitan Yellow Tuff (12ka): eruption of Vesuvius and caldera collapse]

Waste and Wastewater Treatment

Municipal Wastewater
Drinking water

Zeolite filled, water-purification tanks - Denver, CO

Mumpton 1999

Agricultural Applications

Animal nutrition and food additive

Agronomy and Horticulture
A
Aquaculture
lt
Animal-waste Treatment

Mumpton 1999

Zeoponics
Zeoponics
Its
It s a new kind of growth medium
developed by NASA for space travel
Its name is from zeolite and hydroponic
Its a growth medium with nutrients
Its a nutrient delivery system
Its an additive that makes other growth
g
media more effective in growing plants

Zeoponics
See http://www.zeoponix.com/
As a result of a Small Business
Innovative Research contract with
NASA, ZeoponiX, a small company in
Louisville CO
Louisville,
CO, manufactures ZeoProTM,
a combination of a nutrient-charged
zeolite and slowly dissolving substances
that contain phosphorous and other
nutrients
Zeoponics
p
is expected
p
to be applied
pp
on
the International Space Station and in
future missions to extra-terrestrial
bodies, such as Mars and the Moon

ZeoPro is manufactured from a

naturall source off clinoptilolite
li
il li

Ca10(PO4)6(OH)2

Apatite Structure and Formula

OH-, F-, Cl-

Ca+2
Ca+2
Ca+2

PO43-

Ca5(PO4)3(OH,F,Cl)

Clinoptilolite Structure

Adsorption and Catalysis

Mumpton 1999

Nuclear Waste and Fallout

Mumpton 1999

Other Applications
Consumer Products
Medical Applications

Mumpton 1999

Structure of Heulandite-Clinoptilolite

Ten-membered and 8membered tetrahedral

rings form channels
parallel to the c-axis
c-axis.
Small green spheres
represent Na, larger light
blue spheres represent
K, small yellow spheres
represent Ca, large blue
spheres represent H2O
molecules.

(Na,K,Ca0.5)7[Al7Si29O72].22H2O

Sample Zeolite Formulas

Mineral Name

General Formula

Analcime

Na16[Al16Si32O96]16H2O

Chabazite

(Ca0.5,Na,K)4[Al4Si8O24]12H2O

Clinoptilolite

(Na,K)6[Al6Si30O72]20H2O

Erionite

K2(Na,Ca0.5)8[Al10Si26O72]28H2O

Heulandite

(Na K)Ca4[Al9Si27O72]24H2O
(Na,K)Ca

Laumontite

Ca4[Al8Si16O48]18H2O

Mesolite

Na16Ca16[Al48Si72O240]64H2O

Scolecite

Ca8[[Al16Si24O80]]24H2O

Stilbite

NaCa4[Al9Si27O72]30H2O