zeolites andrew raulerson march 12, 2015 g
TRANSCRIPT
ZeolitesAndrew Raulerson
March 12, 2015
http://upload.wikimedia.org/wikipedia/commons/e/e8/ZeolitesUSGOV.jpg
Outline
Introduction Properties Geology/Formation Mining and Processing Production
US Production Synthetics
Production Market Uses Conclusions
Introduction
Zeolite coined by Axel Fredrik Cronstedt in 1756 Zeo – to boil; Lithos – stone
Rapidly heated stilbite and observed steam coming from the rock
Water is adsorbed into the crystal structure
Naturally occurring and synthetic varieties ~40 naturally occurring zeolites
Most common: clinoptilolite, chabazite, and mordenite Over 150 synthetic zeolites
Properties
Only naturally occurring mineral with a negative charge Tectosilicates Ratio of silica and aluminum to oxygen must equal ½ Hardness – 3.5-5.5 Density – 1.0 g/cm3 Specific gravity – 2.0-2.4 g/cm3 Consist of silicon, aluminum, oxygen and
cations Hydrous but water not part of crystal
structure
http://commons.wikimedia.org/wiki/File:Zeolite-ZSM-5-3D-vdW.png
Clinoptilolite chemical formula:
(Na,K,Ca)2-3Al3(Al,Si)2Si13O36·12H2O
Geology/Formation Low grade metamorphic minerals Form from volcanic tuffs and marine
volcanic tuffs Pressure range – 0-2.5 kbar Temperature range - 25°C-250°C
Ideal T range - 27°C-55°C Typically requires interaction of volcanic
glass and saline water Associated with alteration of volcanic tuffs
in alkaline lake deposits pH around 9-10
Requires 50-50,000 years to form
http://commons.wikimedia.org/wiki/File:Metamorphic_Facies_Diagram.png
Mining Conventional open pit methods Overburden removed Ore is blasted or stripped using front-end loaders Shallow deposits are stripped Deep deposits are drilled and blasted
http://www.rotamadencilik.com.tr/production3.html
http://www.bearriverzeolite.com/brz_geology_mining.htm
Processing
Ore is transported to processing plant Crushed, dried, and milled Some is sold after milling If granular materials are needed, they are sieved to remove
the finer materials Granular is sold at this point
Finer materials are used in the production of pellets Addition of binder (kaolin clay typically) then dried
Properties of zeolites may be modified using other chemical methods at the end of processing
Production
World production estimated at 2.7-3.2 Mt/yr World leading producers
China – 1.8-2.2 Mt/yr Republic of Korea – 230,000 t/yr United States – 69,500 t/yr Cuba – 40,000-45,000 t/yr Mexico – 2,000-2,500 t/yr Indonesia – 1,000-2,000 t/yr
Some countries don’t report production Australia, Canada, and South Africa, among others
US Production
Mined in seven states AZ, CA, ID, NV, NM, OR, and TX
Nine companies actively mined in 2013 Bear River Zeolite Zeotech Corporation St. Cloud Mining
http://minerals.usgs.gov/minerals/pubs/commodity/zeolites/myb1-2013-zeoli.pdf
Synthetics
First synthesized in the 1930’s Market didn’t develop until 1960’s
Over 150 varieties synthesized Most common: Zeolite A, Zeolite X, Zeolite Y, and Zeolite ZMS-5
Same properties as natural zeolites Just formed in a lab
Consistent chemical structure No impurities
Production
Hydrothermal treatment of solid or gel aluminosilicate
Crystallization of aluminum hydroxide, sodium hydroxide, and sodium silicate under carefully controlled conditions yields required structure
Ion exchanged to adjust pore size
Dried and processed to activated zeolite powder Some applications require
beads/pellets
http://www.zeolites.eu/downloads/Zeolites.pdf
Market
No major geopolitics involving zeolites Naturals
Price range: $50-$800 per metric ton Bulk of material $100-$230
Synthetics Price: upwards of $1,500 per metric ton
http://minerals.usgs.gov/minerals/pubs/commodity/zeolites/myb1-2013-zeoli.pdf
Uses Chemical sieve
Ion exchange Zeolites are negatively charged (anion) Cations are loosely bound in tunnels Cations are readily knocked out of position and replaced
http://www.aquatechnology.net/conditionerswork.html
Uses - Naturals Decreasing demand: animal feed, pet litter, odor control,
water purification, and wastewater treatment Animal feed
Reduce toxin concentration in liver Remove heavy elements from system Decreased mortality of weaning piglets by reducing effects of
post-weaning diarrhea syndrome Strengthened egg shells when laying hens were treated
Pet litter Effective at adsorbing ammonia and hydrogen sulfide
Water purification Na+ replaces Ca2+ in water
Uses - Synthetics Used in highly specific applications Replaced phosphate compounds in laundry detergent powders in the 1970’s
Accounts for 80% of use of synthetics Acts as a water softener
Hard water impairs the effectiveness of detergents
No harm to environment Break down into naturally occurring aluminosilicate species
Fluid Catalyst Cracking (FCC) 2nd most common use Refining crude petroleum
Drug delivery Can be modified to release drugs in certain conditions for optimal effectiveness in
the body
ReferencesCoOL. 1996. Zeolites. Abbey Newsletter, v. 20, no. 7. http://cool.conservation-us.org/byorg/abbey/an/an20/an20-7/an20-702.html
Cook, T.E., Cilley, W.A., Savitsky, A.C., Wiers, B.H. (1982) Zeolite A hydrolysis and degradation. Environmental Science & Technology, 16:344–350.
CEFIC. 2000. http://www.zeolites.eu/downloads/Zeolites.pdf
Fruijtier-Pölloth, C., 2009, The safety of synthetic zeolites used in detergents: Archives of Toxicology, v. 83, no. 1, p. 23–35, doi: 10.1007/s00204-008-0327-5.
Galleries. http://www.galleries.com/zeolite_group
IHS. https://www.ihs.com/products/zeolites-chemical-economics-handbook.html
MEC. 2013. Zeolites. http://www.mineralseducationcoalition.org/minerals/zeolites
Rimoli, M.G., Rabaioli, M.R., Melisi, D., Curcio, A., Mondello, S., Mirabelli, R., and Abignente, E., 2008, Synthetic zeolites as a new tool for drug delivery:
Journal of Biomedical Materials Research Part A, v. 87A, no. 1, p. 156–164, doi: 10.1002/jbm.a.31763.
TA Instruments. 2007. Measuring Carbon Dioxide Adsorption into Zeolite Structures Using High-Pressure TGA (TGA-HP) http://www.tainstruments.com/pdf/TA359%20Measuring%20Carbon%20Dioxide%20Adsorption%20into%20Zeolite%20Structures%20Using%20High-Pressure%20TGA.pdf
The Wolfe Clinic. Zeolite – Nature’s Detoxifier. http://www.thewolfeclinic.com/index.php/information-and-tools/dr-wolfe-article-archive/223-zeolite-natures-detoxifier
Trckova, M., Matlova, L., Dvorska, L., and Pavlik, I. 2004. Kaolin, bentonite, and zeolites as feed supplements for animals: health advantages and risks. Vet Med. – Czech, v. 49, no. 10. 389-399
Virta, R. 2008. Natural and Synthetic Zeolites. USGS. http://minerals.usgs.gov/mineralofthemonth/zeolites.pdf
Virta, R. 2014. 2013 Minerals Yearbook: Zeolites. USGS Minerals Yearbook. http://minerals.usgs.gov/minerals/pubs/commodity/zeolites/myb1-2013-zeoli.pdf
W. R. Grace & Co. – Conn. 2000. Synthetic Non-fibrous Zeolites Product Stewardship Summary. https://grace.com/en-us/environment-health-and-safety/ProductStewardship/Documents/Zeolites.pdf
http://www.aquatechnology.net/conditionerswork.html
http://www.bearriverzeolite.com/brz_geology_mining.htm
http://www.rotamadencilik.com.tr/production3.html