Environmental Issues 

Affecting Raw Material SelectiAffecting Raw Material Selecti

GM

C

C. Phil

www.GlassIndustryCo
Raw Material Environmental I

• Employee Exposure Employee Exposure

– Handling Dust F

Handling, Dust, F

• Meltin

g Furnace Exhaust Com

ponents

• Solid Waste – Particulate Recycle

Furnace Demolition

• Vendor Concerns 

– Cost / Availability

• O ti i A li ti O

pti

m

ize 

Applications (F O t

(Furnace 

Operat
OSHA / Employee Exposure
“Heavy Metals” Historical Glass Applica

(Introduced as an oxide, 

a metal or other compound for

metal, or other compound for

Element MWT Purpose

Arsenic (As) 74.9 Refining AgentBarium (Ba) 137.9 Glass Former, Sulfate SourCadmium (Cd) 113 9. Colorant ColorantCobalt (Co) 58.9 ColorantCopper (Cu) 62.9 ColorantChromium (Cr) 51 9. Colorant ColorantMercury (Hg) 200.6 Florescent Light Cullet (CoManganese (Mn) 54.9 Colorant, OxidizerNickel (Ni) 57 9. Colorant ColorantLead (Pb) 208.0 Glass ModifierAntimony (Sb) 120.9 Refining AgentSelenium (Se) 79 9. Colorant Colorant, Decolorizer DecolorizerZinc (Zn) 63.9 Colorant / Opacifier Comp
Minor Constituents

• Colorants

Chrome

, Selenium

, Nickel

• Refining Agents

Arsenic, Antimony, Sulfates, Nitrates

• Concerns:

Respirable Dust Respirable VaporsFurnace Stack EmissionsSolid Waste Disposal Solid Waste Disposal

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

Glass Chemistry Modification

• Arsenic to Antimony or alternate Refining Syste

• Nitrates to Nitrates to MnO in Cold Top Electric Melters

2 in Cold Top Electric Melters

• Selenium Metal to Selenides or Selenates• Lead to Barium or Zirconia Composition Modif• Boron Free Boron Free Reinforcing Fiber Glass Reinforcing Fiber Glass• Reduced Boron - Insulating Fiber Glass Compo
Glass Furnace Emissions

• Particulate (Condensate / Dust) (Condensate

/ Dust)

• SO

X

• NO

X (Combustion, Nitrates)

• CO• HAP’s (Volatile Heavy Metals)• Green House Gases (Combustion, Carbo

CO

2 or “Carbon Equivalent Units “ (CEU’s)


Furnace Role in Particulate Emis

Na+ (NaOH) / HBO

2 Volatilization 

= Higher Particulate in Stack Emissions

Greater Volatilization from:

Raw Material Dusting - Borates, Soda Ash, Salt Cake 

Hi hg

her M lt e Sf T t ur

face 

Tempera

ture

Higher Melt Surface Area - Foam, Froth, Bubblers

Higher Atmospheric Gas Velocity (firing rates)

Atmospheric Chemistry

Higher H2O partial pressureHigher CO partial pressure Higher CO partial pressure

Lower % Cullet / More Raw MaterialsNaOH Batch Wetting

Batch “Redox” controls SO

4

= Retention / SO

X Emission 
Combustion for NO

X Contr

• Melt Surface Atmosphere 

Influences Glass Redox & Volatilization

• N B dL V P H M l Na, 

B an

d

Low 

Vapor 

Pressure 

Heavy 

Metals

Reminder - 100 % of N in Nitrates becomes N
Selenium Alternatives

Ruud Beerkins 
Particulate Capture Recycli
Particulate / Scrubber 

Recycling Captured Material IsRecycling Captured Material Iss

• Ch i t C i t Chemis

try 

Consis

tency

– R d O id R

e

dox, 

O

xides

• Scrubber Reagent Scrubber Reagent Considerations Considerations

Effective Stoichiometry (Temperature Cost Handling Fe Cost, Handling, Fe

2

O

3

• Dr

y Introduction - Particle Size

, gg A lome

• Wet Introduction

– Concentration, Hand
Particulate Capture/Recyc

• Particulate Chemistry Variability• SOX S bbi / R t R t V i bilit SOX

Scrubbing 

/

Reagen

t

R

a

te 

Variabilit

• Particle Size Requires Agglomeration
National Emission Standard for Hazardous Air Po

Batch Formulations which Incorporate any of 7 Regulated 

Must Meet (NSPS) Must Meet (NSPS) 0 2 lb . . Particulate per ton of glass mel

Particulate per ton of glass mel

or M-29 test to confirm <0.02 lb. total HAP’s per ton of glass 
Bulk Material Issues -

Sand, Soda Ash, Limestone, Dolomite, Feld

• TC t race 

Componen

t

s

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

P ti l Si C i Parti

cle Size 

Compromises
Trace Volatile HM Condensati
Recycled “Post Consumer” C

• Validates the Recyclability / Sustainability of G

• Reduces CO

2 Emissions (by Process and Fuel Red

• Quality Concerns

Color (Colorants, Sulfur)Glass Types (Chemistry Differences)

CaO/MgO, Al

2

O

3, B

2

O3 ,Sulfur

Inappropriate Categories (Mercury VaporInappropriate Categories (Mercury VaporNon-Glass Contaminant SolidsOrganic (COD) Contaminant levels

• Formalize Comprehensive Quantifiable Speci

Mutual Acceptance by Vendor & Glass Manufac
Model Toxics in Packaging Legislatio

Toxics in Packaging Clearinghouse (TPToxics in Packaging Clearinghouse (TP

• 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 

Legislation

• Legislation has been successfully adopted by > nineteen states • Any package or packaging component can not have any of the four met

intentionally introduced

• Packaging components may include coatings, inks and labels (such as A

• The incidental presence of the metals must be reduced to 100 parts per 
Recycled Cullet Reminder

Mercury – Florescent Lighting Glass CulletAs 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, 

Historica

l Reminders:

Lead

- historically from the furnace exhaust vapors in the manufactu

CRT glass or Lead Crystal tableware. 

Lead Foil over Wine Bottle ClosuresLead Based ACL Cullet
Raw Material Substitution Exam

Calumite

• Calcium-Alumino-Silicate

by-product from blast furnaces producing Iro

• Partial Substitution Partial Substitution for

Sand, RO Carbonates, Alumina Sources, and 

• Provides More Effective Refining Form of Sulfur (

• Reduces Process CO

2 Emissions ( 

Limestone, Dolom

• Reduces Melting Energy by Increasing Pull Poten• Potentially Represents “Recycled Content” in gla
Calumite “Slag” Environment

Considerations

• Amber Container Glass

@ 8.3 % of Batch WeightReduced SO

X/Ton by 46 %

Reduced Process CO

2 Reduced Process CO2/Ton by 17 %

Melting Energy Savings by Electric Boost 

• Architectural Float Glass

@ 3.7 % of Batch % of Batch WeightReduced Process CO

2/Ton by 9 %

Reduced Natural Gas CO

2/Ton by 4 %
Summary

• Employee Exposure Limits – Monitor & Contro

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

& 

• Recognize Raw Materials Role in Furnace Emis• Furnace Operational Variables Influence Emiss

• Refining Mechanisms - Improvements & Optim

• Vendors face Environmental Requirements wh

Influence their products Cost & Availability

• Most of these issues are common and many co

addressed collectively by the Glass Industry