Environmental Issues Affecting Raw Material SelectionAffecting Raw Material Selection

GMIC Workshop

Columbus, OH

O t 20 2011Oct. 20, 2011

C. Philip Ross – GICI

www.GlassIndustryConsulting.com

Raw Material Environmental Issues

• Employee Exposure – Handling Dust FumesEmployee Exposure Handling, Dust, Fumes

• Melting Furnace Exhaust Componentsg p

• Solid Waste – Particulate Recycle

Furnace Demolition

• Vendor Concerns – Cost / Availability

O ti i A li ti (F O ti )• Optimize Applications (Furnace Operations)

OSHA / Employee Exposures

“Heavy Metals” Historical Glass Applications (Introduced as an oxide a metal or other compound form)(Introduced as an oxide, a metal, or other compound form)

Element MWT Purpose

Arsenic (As) 74.9 Refining Agent

Barium (Ba) 137.9 Glass Former, Sulfate Source

Cadmium (Cd) 113 9 ColorantCadmium (Cd) 113.9 Colorant

Cobalt (Co) 58.9 Colorant

Copper (Cu) 62.9 Colorant

Chromium (Cr) 51 9 ColorantChromium (Cr) 51.9 Colorant

Mercury (Hg) 200.6 Florescent Light Cullet (Contaminant)

Manganese (Mn) 54.9 Colorant, Oxidizer

Nickel (Ni) 57 9 ColorantNickel (Ni) 57.9 Colorant

Lead (Pb) 208.0 Glass Modifier

Antimony (Sb) 120.9 Refining Agent

Selenium (Se) 79 9 Colorant DecolorizerSelenium (Se) 79.9 Colorant, Decolorizer

Zinc (Zn) 63.9 Colorant / Opacifier Component

Minor Constituents

• ColorantsChrome, Selenium, Nickel, ,

• Refining AgentsArsenic, Antimony, Sulfates, Nitrates

• Concerns:Respirable Dust Respirable VaporsFurnace Stack EmissionsSolid Waste DisposalSolid Waste Disposal

Trace levels of Volatile Heavy Metals condense in Exhaust systemand will result in concerns later with demolition / disposal

Raw Material SubstitutionsGlass Chemistry Modifications

• Arsenic to Antimony or alternate Refining Systems

• Nitrates to MnO in Cold Top Electric MeltersNitrates to MnO2 in Cold Top Electric Melters

• Selenium Metal to Selenides or Selenates

• Lead to Barium or Zirconia Composition Modifications

• Boron Free Reinforcing Fiber Glass• Boron Free Reinforcing Fiber Glass

• Reduced Boron - Insulating Fiber Glass Compositions

Glass Furnace Emissions

• Particulate (Condensate / Dust)• Particulate (Condensate / Dust)

• SOX

• NOX (Combustion, Nitrates)

• CO• CO

• HAP’s (Volatile Heavy Metals)

• Green House Gases (Combustion, Carbonates)CO2 or “Carbon Equivalent Units “ (CEU’s)

Furnace Role in Particulate EmissionsNa+ (NaOH) / HBO2 Volatilization

= Higher Particulate in Stack Emissions

Greater Volatilization from:Raw Material Dusting - Borates, Soda Ash, Salt Cake (dry batch)Hi h M lt S f T tHigher Melt Surface TemperatureHigher Melt Surface Area - Foam, Froth, BubblersHigher Atmospheric Gas Velocity (firing rates)Atmospheric Chemistry

Higher H2O partial pressureHigher CO partial pressureHigher CO partial pressure

Lower % Cullet / More Raw MaterialsNaOH Batch Wetting

Batch “Redox” controls SO4= Retention / SOX Emission Balance

Combustion for NOX Control • Melt Surface Atmosphere

Influences Glass Redox & VolatilizationN B d L V P H M l• Na, B and Low Vapor Pressure Heavy Metals

Reminder - 100 % of N in Nitrates becomes NOX

Selenium Alternatives

Ruud Beerkins - TNO

Particulate Capture Recycling

Particulate / Scrubber Recycling Captured Material IssuesRecycling Captured Material Issues

Ch i t C i t R d O id• Chemistry Consistency – Redox, Oxides

• Scrubber Reagent Considerations• Scrubber Reagent ConsiderationsEffective Stoichiometry (Temperature Range)Cost Handling Fe OCost, Handling, Fe2O3

• Dry Introduction - Particle Size, Agglomerationy , gg

• Wet Introduction – Concentration, Handling

Particulate Capture/Recycle

• Particulate Chemistry Variability

SOX S bbi / R t R t V i bilit• SOX Scrubbing / Reagent Rate Variability

• Particle Size Requires Agglomeration

National Emission Standard for Hazardous Air Pollutants Batch Formulations which Incorporate any of 7 Regulated HM’s

Must Meet (NSPS) 0 2 lb Particulate per ton of glass melted)Must Meet (NSPS) 0.2 lb. Particulate per ton of glass melted)or M-29 test to confirm <0.02 lb. total HAP’s per ton of glass melted

Bulk Material Issues -Sand, Soda Ash, Limestone, Dolomite, Feldspathic

T C t• Trace ComponentsAs, Cl, SO4 in Soda AshCd in LimestonePyrite (S=) in ClaysPb, Ba, Hg in Cullet

• Tableware & Solar Glass - Low Iron

• Frac Sand Price / Availability

P ti l Si C iParticle Size Compromises

Trace Volatile HM Condensation

Recycled “Post Consumer” Cullet• Validates the Recyclability / Sustainability of Glass

• Reduces CO2 Emissions (by Process and Fuel Reductions)

• Quality ConcernsColor (Colorants, Sulfur)

lGlass Types (Chemistry Differences)CaO/MgO, Al2O3, B2O3 ,Sulfur

Inappropriate Categories (Mercury Vapor)Inappropriate Categories (Mercury Vapor)Non-Glass Contaminant SolidsOrganic (COD) Contaminant levels

• Formalize Comprehensive Quantifiable Specifications Mutual Acceptance by Vendor & Glass Manufacturer

Model Toxics in Packaging LegislationToxics in Packaging Clearinghouse (TPCH)Toxics in Packaging Clearinghouse (TPCH)

• MTPL was developed to reduce the amount ofHg MHg - Mercury, Pb - Lead, Cd - Cadmium, and Cr+6 - Hexavalent Chromium

• Toxics in Packaging Clearinghouse formed to promote the Model Toxics in Packaging Legislation

• Legislation has been successfully adopted by > nineteen states

• Any package or packaging component can not have any of the four metals intentionally introduced

• Packaging components may include coatings, inks and labels (such as ACL’s)

• The incidental presence of the metals must be reduced to 100 parts per million

Recycled Cullet RemindersMercury – Florescent Lighting Glass Cullet

As manufactured – Glass initially has no mercury,

In use, the glass surface becomes impregnated with low levels of Hg Extremely low vapor pressure results in 100 % volatilization into exhaust

Properly processing required to remove Hg before re-melting,

Historical Reminders:Lead - historically from the furnace exhaust vapors in the manufacturing of CRT glass or Lead Crystal tableware.

Lead Foil over Wine Bottle ClosuresLead Based ACL Cullet

Raw Material Substitution ExampleCalumiteCalumite

• Calcium-Alumino-Silicate

by-product from blast furnaces producing Iron

• Partial Substitution for• Partial Substitution for

Sand, RO Carbonates, Alumina Sources, and Sulfates

• Provides More Effective Refining Form of Sulfur (S=)

• Reduces Process CO2 Emissions (Limestone, Dolomite)2 ( )

• Reduces Melting Energy by Increasing Pull Potential

• Potentially Represents “Recycled Content” in glass?

Calumite “Slag” Environmental ConsiderationsConsiderations

• Amber Container Glass@ 8.3 % of Batch WeightReduced SOX/Ton by 46 %Reduced Process CO2/Ton by 17 %Reduced Process CO2/Ton by 17 %Melting Energy Savings by Electric Boost

• Architectural Float Glass@ 3.7 % of Batch Weight@ 3.7 % of Batch WeightReduced Process CO2/Ton by 9 %Reduced Natural Gas CO2/Ton by 4 %

Summary

• Employee Exposure Limits – Monitor & Control

• Look Closer for Heavy Metal Contents (RM’s & Cullet)Look Closer for Heavy Metal Contents (RM s & Cullet)

• Recognize Raw Materials Role in Furnace Emissions

• Furnace Operational Variables Influence Emissions

• Refining Mechanisms - Improvements & Optimization

• Vendors face Environmental Requirements which will Influence their products Cost & Availability

• Most of these issues are common and many could be addressed collectively by the Glass Industry