1. Zeolites Andrew Raulerson March 12, 2015 http://upload.wikimedia.org/wikipedia/commons/e/e8/ZeolitesUSGOV.jp g

2. Outline  Introduction  Properties  Geology/Formation  Mining and Processing  Production  US Production  Synthetics  Production  Market  Uses  Conclusions

3. 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

4. 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/cm 3  Specific gravity – 2.0-2.4 g/cm 3  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) 2-3 Al 3 (Al,Si)2Si 13 O 36 ·12H 2 O

5. 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

6. 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

7. 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

8. 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

9. 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

10. 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

11. 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

12. 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

13. 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

14. 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 Ca 2+ in water

15. 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)  2 nd most common use  Refining crude petroleum  Drug delivery  Can be modified to release drugs in certain conditions for optimal effectiveness in the body

16. References CoOL. 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

17. Questions?