Environmental Issues. GMIC Workshop Columbus, OH Ot20 Oct. 20, C. Philip Ross GICI.

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1 Environmental Issues Affecting Raw Material Selection GMIC Workshop Columbus, OH Ot20 Oct. 20, 2011 C. Philip Ross GICI

2 Raw Material Environmental Issues Employee Exposure Handling, Dust, Fumes Melting Furnace Exhaust Components Solid Waste Particulate Recycle Furnace Demolition Vendor Concerns Cost / Availability Optimize i Applications (Furnace Operations)

3 OSHA / Employee Exposures

4 Heavy Metals Historical Glass Applications (Introduced as an oxide, a metal, or other compound form) Element MWT Purpose Arsenic (As) 74.9 Refining Agent Barium (Ba) Glass Former, Sulfate Source Cadmium (Cd) Colorant Cobalt (Co) 58.9 Colorant Copper (Cu) 62.9 Colorant Chromium (Cr) 51.9 Colorant Mercury (Hg) Florescent Light Cullet (Contaminant) Manganese (Mn) 54.9 Colorant, Oxidizer Nickel (Ni) 57.9 Colorant Lead (Pb) Glass Modifier Antimony (Sb) Refining Agent Selenium (Se) Colorant, Decolorizer Zinc (Zn) 63.9 Colorant / Opacifier Component

5 Minor Constituents Colorants Chrome, Selenium, Nickel Refining Agents Arsenic, Antimony, Sulfates, Nitrates Concerns: Respirable Dust Respirable Vapors Furnace Stack Emissions Solid Waste Disposal Trace levels of Volatile Heavy Metals condense in Exhaust system and will result in concerns later with demolition / disposal

6 Raw Material Substitutions Glass Chemistry Modifications Arsenic to Antimony or alternate Refining Systems Nitrates to MnO 2 in Cold Top Electric Melters Selenium Metal to Selenides or Selenates Lead to Barium or Zirconia Composition Modifications Boron Free Reinforcing Fiber Glass Reduced Boron - Insulating Fiber Glass Compositions

7 Glass Furnace Emissions Particulate (Condensate / Dust) SO X NO X (Combustion, Nitrates) CO HAP s (Volatile Heavy Metals) Green House Gases (Combustion, Carbonates) CO 2 or Carbon Equivalent Units (CEU s)

10 Furnace Role in Particulate Emissions Na+ (NaOH) / HBO 2 Volatilization = Higher Particulate in Stack Emissions Greater Volatilization from: Raw Material Dusting - Borates, Soda Ash, Salt Cake (dry batch) Higher Melt ltsurface Temperature Higher Melt Surface Area - Foam, Froth, Bubblers Higher Atmospheric Gas Velocity (firing rates) Atmospheric Chemistry Higher H 2 O partial pressure Higher CO partial pressure Lower % Cullet / More Raw Materials NaOH Batch Wetting Batch Redox controls SO 4= Retention / SO X Emission Balance

11 Combustion for NO X Control Melt Surface Atmosphere Influences Glass Redox & Volatilization Na, B and Low Vapor Pressure Heavy Metals Reminder % of N in Nitrates becomes NO X

12 Selenium Alternatives Ruud Beerkins - TNO

13 Particulate Capture Recycling

14 Particulate / Scrubber Recycling Captured Material Issues Chemistry Consistency Redox, Oxides Scrubber Reagent Considerations Effective Stoichiometry (Temperature Range) Cost, Handling, Fe 2 O 3 Dry Introduction - Particle Size, Agglomeration Wet Introduction Concentration, Handling

15 Particulate Capture/Recycle Particulate Chemistry Variability SOX Scrubbing / Reagent Rate Variability Particle Size Requires Agglomeration

16 National Emission Standard for Hazardous Air Pollutants Batch Formulations which Incorporate any of 7 Regulated HM s Must Meet (NSPS) 02lb 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

17 Bulk Material Issues - Sand, Soda Ash, Limestone, Dolomite, Feldspathic Trace Components As, Cl, SO 4 in Soda Ash Cd in Limestone Pyrite (S = ) in Clays Pb, Ba, Hg in Cullet Tableware & Solar Glass - Low Iron Frac Sand Price / Availability Particle Size Compromises

18 Trace Volatile HM Condensation

19 Recycled Post Consumer Cullet Validates the Recyclability / Sustainability of Glass Reduces CO 2 Emissions (by Process and Fuel Reductions) Quality Concerns Color (Colorants, Sulfur) Glass Types (Chemistry Differences) CaO/MgO, Al 2 O 3, B 2 O 3, Sulfur Inappropriate Categories (Mercury Vapor) Non-Glass Contaminant Solids Organic (COD) Contaminant levels Formalize Comprehensive Quantifiable Specifications Mutual Acceptance by Vendor & Glass Manufacturer

20 Model Toxics in Packaging Legislation Toxics in Packaging Clearinghouse (TPCH) MTPL was developed to reduce the amount of Hg - 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 Reminders Mercury Florescent Lighting Glass Cullet As manufactured

low levels of Hg Extremely low vapor pressure results in 100 % volatilization into

Reminders: Lead - historically from the furnace exhaust vapors in the manufacturing

21 Recycled Cullet Reminders Mercury 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 Closures Lead Based ACL Cullet

22 Raw Material Substitution Example Calcium-Alumino-Silicate Calumite by-product from blast furnaces producing Iron Partial Substitution for Sand, RO Carbonates, Alumina Sources, and Sulfates Provides More Effective Refining Form of Sulfur (S = ) Reduces Process CO 2 Emissions (Limestone, Dolomite) Reduces Melting Energy by Increasing Pull Potential Potentially Represents Recycled Content in glass?

23 Calumite Slag Environmental Considerations Amber Container 8.3 % of Batch Weight Reduced SO X /Ton by 46 % Reduced Process CO 2 /Ton by 17 % Melting Energy Savings by Electric Boost Architectural Float 3.7 %ofbatchweight Reduced Process CO 2 /Ton by 9 % Reduced Natural Gas CO 2 /Ton by 4 %

24 Summary Employee Exposure Limits Monitor & Control 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

EPA Primary. (mg/l as CaCO3) (mg/l as CaCO3)

EPA Primary. (mg/l as CaCO3) (mg/l as CaCO3) NORTH TEXAS MUNICIPAL WATER DISTRICT - Wylie Water Analysis Jan-2018 Mineral Analysis Raw Treated Standards Residue on Evaporation 412 456 500 1000 Silica (SiO2) 3.63 3.41 Iron (Fe) 0.378 0.259 0.3 0.3