Existing and Potential Applications of

Zeolites in Water Treatment and

Agriculture

Raul F. Lobo
Center for Catalytic Science and Technology
Dept. of Chemical Engineering
University of Delaware

Oct. 16, 2007

 Zeolites
• Crystalline aluminosilicate with a four
connected tetrahedral framework structure
enclosing cavities occupied by large ions and
guest molecules with considerable freedom of
movement, permitting ion exchange and
reversible dehydration
• Gismondine: |Ca2+4 (H2O)16|[Al8Si8O32]–GIS
• Key elements:
– Framework
– Cations
– Guest Molecules
Zeolite Gismondine (GIS)
Large Cages with Small Pore
Windows

Zeolite Chabazite
 Pore Systems
• Dimensionality and size of zeolite pores
define many of its properties
– Size of smallest window determine size of
molecules that can enter/leave the zeolite
– Dimensionality affect many properties such as
diffusion, pore blocking, etc.
– Pore intersections act like cages
– Classification:
• Small 8-ring 4Å Zeolite A
• Medium 10-ring 5.6 Å ZSM-5
• Large 12-ring 7.8 Å USY
• Extra-large pore +12-ring >8Å UTD-1
 Framework Composition
• Structure is what make zeolites unique,
chemical composition can greatly affect their
properties
– Silica zeolites (SiO2–CHA). Very hydrophobic,
covalent bonding dominates, no other interactions
besides dispersion forces
– High-silica Zeolites (Si/Al>10). Less hydrophobic,
H-bond or eletrostatic forces important
– Low-silica zeolites (Na+[SiAlO4]–CHA) Very
hydrophilic, bonding more ionic, H-bond-
electrostatic interactions dominate
 Ion Exchange

• Extra-framework cations can be ion

exchanged in aqueous solutions
– Zeo-(Na+)2 + Ca2+ (aq) ⇒ Zeo-Ca2+ + 2 Na+ (aq)
– Di and trivalent cations are adsorbed
preferentially
– Large cations are ion exchange
preferentially (NH4>Na+)
 Natural Zeolites

• Long history of use for soil remediation,

synthetic soil, amendment for soil, animal
food additive
• Inexpensive
– 0.5-0.12 $/kg
• Available in large quantities in US, Europe
and many other countries
– Clinoptilolite is the most commonly used zeolite
due to large surface deposits of good quality
(80%+ zeolite)
– Over 40 different structures found in nature
 Agriculture

• Amendment for sandy and low clay content

soils
• Quantity:8-15 ton/hectare
• Improves retention of nitrogen
– Can be pretreated with ammonia for slow release
effects
• Reduces leaching of metals from soil
• Improves water retention and soil porosity
 Phytoremediation

• Zeolites adsorb metal cations from soils

– Reduction in local concentration allows for
plants to grow
• Increase quantity of microorganisms in
soil
• Accelerate nitrogen fixation by releasing
NH4+ slowly
 Animal Feed Additive

• Dozens of studies documenting the

effect of zeolites as food additive
– Generally, an improvement in health of the
animals is observed (1-3% w/w)
– Reduction of odors as zeolites sequester
NH3
– Few studies address relationship between
molecular structure and physiological effect
 Water Purification

• Zeolites selectively remove ammonium and

2+ cations from aqueous solutions
– Sequestration of Zn2+, Cd2+ and other ions.
– It is a one-time use unless expensive equipment is
used for re-exchange with Na+.
– Purification of mining effluent waters
• Use of zeolites is widespread in municipal
facilities to remove ammonium ions to
acceptable limits.
 Outlook

• There appears to be no radical new

technologies that are being developed with
zeolites that could affect agricultural
production in poor countries
• Niches of opportunity may be present where
local concentrations of metal ions affect
agricultural output
• Water purification is an area of opportunity
but technology and applications already exist