Environmental IssuesAffecting Raw Material SelectionAffectingRawMaterialSelectionGMIC WorkshopColumbus, OHO t20 2011ct.20,2011C. Philip Ross – GICIwww.GlassIndustryConsulting.comRaw Material Environmental Issues•Employee Exposure–Handling Dust FumesEmployeeExposureHandling,Dust,Fumes•MeltingFurnace ExhaustComponents•Solid Waste– Particulate RecycleFurnace Demolition•Vendor Concerns–Cost / AvailabilityO ti i A li ti(F O ti )•OptimizeApplications(FurnaceOperations)OSHA / Employee Exposures“Heavy Metals” Historical Glass Applications(Introducedas anoxideametal or other compound form),metal,orothercompoundform)ElementMWTPurposeArsenic (As) 74.9 Refining AgentBarium (Ba) 137.9 Glass Former, Sulfate SourceCadmium(Cd)113 9Colorant.ColorantCobalt (Co) 58.9ColorantCopper (Cu) 62.9ColorantChromium(Cr)51 9Colorant.ColorantMercury (Hg) 200.6Florescent Light Cullet(Contaminant)Manganese (Mn) 54.9Colorant,OxidizerNickel(Ni)57 9Colorant.ColorantLead (Pb) 208.0 Glass ModifierAntimony (Sb) 120.9 Refining AgentSelenium(Se)79 9ColorantDecolorizer.Colorant,DecolorizerZinc (Zn) 63.9Colorant/ Opacifier ComponentMinor Constituents•ColorantsChrome,Selenium,Nickel•Refining AgentsArsenic, Antimony, Sulfates, Nitrates•Concerns:Respirable DustRespirable VaporsFurnace Stack EmissionsSolid Waste DisposalSolidWasteDisposalTrace levels of Volatile Heavy Metals condense in Exhaust systemand will result in concerns later with demolition / disposalRaw Material SubstitutionsGlass Chemistry Modifications•Arsenic toAntimony or alternate Refining Systems•Nitrates toMnOin Cold Top ElectricMeltersNitratesto2inColdTopElectricMelters•Selenium Metal toSelenides or Selenates•Lead toBarium or Zirconia Composition Modifications•Boron FreeReinforcing Fiber GlassBoronFreeReinforcingFiberGlass•ReducedBoron - Insulating Fiber Glass CompositionsGlass Furnace Emissions•Particulate(Condensate / Dust)(Condensate/Dust)•SOX•NOX(Combustion, Nitrates)•CO•HAP’s(Volatile Heavy Metals)•Green House Gases(Combustion, Carbonates)CO2or “Carbon Equivalent Units “ (CEU’s)Furnace Role in Particulate EmissionsNa+ (NaOH) / HBO2Volatilization= Higher Particulate in Stack EmissionsGreater Volatilizationfrom:Raw Material Dusting- Borates, Soda Ash, Salt Cake(dry batch)Hi hM ltSf T tghereurfaceTemperatureHigherMelt Surface Area- Foam, Froth, BubblersHigherAtmospheric Gas Velocity(firing rates)Atmospheric ChemistryHigher H2O partial pressureHigher CO partial pressureHigherCOpartialpressureLower % Cullet/ More Raw MaterialsNaOHBatch WettingBatch “Redox” controls SO4=Retention / SOXEmission BalanceCombustion for NOXControl•Melt Surface AtmosphereInfluences Glass Redox & VolatilizationN B dL V P H M l•Na,BandLowVaporPressureHeavyMetalsReminder - 100 % of N in Nitrates becomes NOXSelenium AlternativesRuud Beerkins - TNOParticulate Capture RecyclingParticulate / ScrubberRecycling Captured Material IssuesRecyclingCapturedMaterialIssuesCh i t C i tR d O id•ChemistryConsistency–Redox,Oxides•Scrubber ReagentConsiderationsScrubberReagentConsiderationsEffective Stoichiometry(Temperature Range)Cost Handling FeOCost,Handling,Fe23•DryIntroduction - Particle Size,Alomerationgg•Wet Introduction–Concentration, HandlingParticulate Capture/Recycle•Particulate Chemistry VariabilitySOX S bbi / R t R t V i bilit•SOXScrubbing/ReagentRateVariability•Particle Size Requires AgglomerationNationalEmissionStandard forHazardousAirPollutantsBatchFormulations which Incorporate anyof 7Regulated HM’sMust Meet (NSPS)0 2 lbParticulate per ton of glass melted)MustMeet(NSPS)..Particulatepertonofglassmelted)orM-29 test to confirm <0.02 lb.total HAP’s per ton of glass meltedBulk Material Issues -Sand, Soda Ash, Limestone, Dolomite, FeldspathicTC t•raceComponentsAs, Cl, SO4in Soda AshCd in LimestonePyrite (S=) in ClaysPb, Ba, Hg in Cullet• Tableware & Solar Glass - Low Iron• Frac SandPrice / AvailabilityP ti l Si C iParticleSizeCompromisesTrace Volatile HM CondensationRecycled “Post Consumer” Cullet•Validates the Recyclability/ Sustainabilityof Glass•ReducesCO2Emissions(by Process and Fuel Reductions)•Quality ConcernsColor (Colorants, Sulfur)lGass Types(Chemistry Differences)CaO/MgO, Al2O3, B2O3 ,SulfurInappropriate Categories (Mercury Vapor)InappropriateCategories(MercuryVapor)Non-Glass Contaminant SolidsOrganic (COD) Contaminant levels•Formalize ComprehensiveQuantifiableSpecificationsMutualAcceptance by Vendor & Glass ManufacturerModel Toxics in Packaging LegislationToxics in Packaging Clearinghouse (TPCH)ToxicsinPackagingClearinghouse(TPCH)•MTPLwas developed to reduce the amount ofHgM-ercury,Pb- Lead,Cd- Cadmium, andCr+6- Hexavalent Chromium•Toxics in Packaging Clearinghouseformed to promote theModel Toxics in PackagingLegislation•Legislation has been successfullyadopted by > nineteen states•Any package or packaging componentcan nothaveanyof thefour metalsintentionallyintroduced•Packaging components may includecoatings,inks and labels(such as ACL’s)•Theincidentalpresenceof the metals must be reduced to 100 parts per millionRecycled Cullet RemindersMercury– Florescent Lighting Glass CulletAs manufactured– Glass initially has no mercury,In use, the glass surface becomesimpregnatedwith low levels of HgExtremely low vapor pressure results in 100 % volatilization into exhaustProperly processing required to remove Hg before re-melting,HistoricalReminders:Lead-historically from the furnace exhaust vapors in the manufacturing ofCRT glassorLead Crystaltableware.Lead Foil over Wine Bottle ClosuresLead Based ACL CulletRaw Material Substitution ExampleCalumite•Calcium-Alumino-Silicateby-product from blast furnacesproducing Iron•Partial SubstitutionforPartialSubstitutionSand, RO Carbonates, Alumina Sources, and Sulfates•Provides More Effective RefiningForm of Sulfur (S=)•Reduces Process CO2Emissions(Limestone, Dolomite))•Reduces Melting Energyby Increasing Pull Potential•Potentially Represents “Recycled Content” in glass?Calumite “Slag” EnvironmentalConsiderations•Amber ContainerGlass@ 8.3 % of Batch WeightReduced SOX/Tonby 46 %ReducedProcess CO2/Tonby17 %ReducedProcessCO2Melting Energy Savings by Electric Boost•Architectural FloatGlass@3.7% of BatchWeight%ofBatchReduced Process CO2/Tonby9 %Reduced Natural Gas CO2/Tonby4 %Summary•Employee Exposure Limits– Monitor & Control•Look Closer forHeavy Metal Contents(RM’& Cullet)LookCloserforHeavyMetalContentss&Cullet)•Recognize Raw MaterialsRole in Furnace Emissions•Furnace Operational VariablesInfluence Emissions•Refining Mechanisms- Improvements &Optimization•VendorsfaceEnvironmental Requirementswhich willInfluence their products Cost & Availability•Most of theseissues are commonand many could beaddressed collectively by the Glass Industry