Zeolites Andrew Raulerson March 12, 2015 g.

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

Questions?