Existing and Potential Applications of Zeolites in Water Treatment and Agriculture Raul F.

Center for Catalytic Science and Technology

Dept. of Chemical Engineering University of Delaware

Oct. 16, 2007

• 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 Medium Large Extra-large pore 8-ring 10-ring 12-ring +12-ring 4Å 5.6 Å 7.8 Å >8Å Zeolite A ZSM-5 USY 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-bondelectrostatic 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

• 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

• 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.

• 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

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