Garry Mokry Glass

8/6/2019 Garry Mokry Glass

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GLASS PLANTSGLASS PLANTS

EPA Region 6 State & LocalEPA Region 6 State & Local Air Inspector Workshop Air Inspector Workshop

February 27, 2008February 27, 2008

Garry MokryGarry MokryEPA Region 6EPA Region 6

[email protected]@epa.gov , 214, 214--6565--74297429


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O utlineO utline

History of glassHistory of glassBasic chemistryBasic chemistry

Types of glassTypes of glassManufacturing processesManufacturing processes

Air pollutants Air pollutants

Emissions controlsEmissions controlsClean Air Act regulationsClean Air Act regulations


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D efinition of GlassD efinition of Glass

A deposited film of silicon dioxide with A deposited film of silicon dioxide withadditives to adjust coefficient of thermaladditives to adjust coefficient of thermalexpansion, color, conductivity, and melting pointexpansion, color, conductivity, and melting pointgenerally doped with boron, or phosphorus, or generally doped with boron, or phosphorus, or both.both.

Glass is a state of matter, not a particular Glass is a state of matter, not a particular substance. It is an amorphous solid that issubstance. It is an amorphous solid that iscooled to rigidity without crystallizing.cooled to rigidity without crystallizing.


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History of GlassmakingHistory of Glassmaking

O ldest manufactured substance in theO ldest manufactured substance in theworldworld

Archaeologists have found glass Archaeologists have found glasscontainers & jars dating back to 1500 B.C.containers & jars dating back to 1500 B.C.Exact method of discovery is a mysteryExact method of discovery is a mysteryEarly discoveries that the temperature of Early discoveries that the temperature of fires combined with powdered obsidianfires combined with powdered obsidian(natural glass) & alkali resulted in a glassy(natural glass) & alkali resulted in a glassyresidueresidue


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GlassGlass- -blowingblowing

GlassGlass- -blowing originated in Syria around theblowing originated in Syria around the11 stst century B.C. It was taken along trade routescentury B.C. It was taken along trade routesto other parts of the Roman Empire. Europeansto other parts of the Roman Empire. Europeans

used a potashused a potash- -lime mixture to form glass thatlime mixture to form glass thatwas used to make stained glass windows.was used to make stained glass windows.

In the 14In the 14 thth and 15and 15 thth centuries, Venetianscenturies, Venetians

developed a brilliant, colorless glass made fromdeveloped a brilliant, colorless glass made fromsilica and purified soda. By the 17silica and purified soda. By the 17 thth century,century,British glassmakers developed crystal.British glassmakers developed crystal.


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K nown as sodaK nown as soda- -lead glass, crystallead glass, crystalcontains lead oxide instead of lime.contains lead oxide instead of lime.

Addition of lead increases the refractive Addition of lead increases the refractiveindex, making it sparkle and also making itindex, making it sparkle and also making itclearer, heavier, and less likely to fractureclearer, heavier, and less likely to fracturewhen etched or carved.when etched or carved.


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Crystal is actually a misnomer. InCrystal is actually a misnomer. Inscientific terms, a crystal is a material withscientific terms, a crystal is a material withan ordered structure. All glass, includingan ordered structure. All glass, includingcrystal, has a long range disorder becausecrystal, has a long range disorder becauseof its status as an intermediate stateof its status as an intermediate statebetween ordered solid and disorderedbetween ordered solid and disorderedliquid.liquid.


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Early glass derived its color fromEarly glass derived its color fromimpurities that were present when theimpurities that were present when theglass was formed. For example, blackglass was formed. For example, blackbottle glass was a dark brown or greenbottle glass was a dark brown or greenglass, first produced in 17glass, first produced in 17 thth centurycenturyEngland. This glass was dark due to theEngland. This glass was dark due to theeffects of the iron impurities in the sandeffects of the iron impurities in the sandused to make the glass and the sulfur fromused to make the glass and the sulfur fromthe smoke of the burning coal used to meltthe smoke of the burning coal used to meltthe glass.the glass.


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Glass is colored by purposely introducingGlass is colored by purposely introducing

minerals or purified metal salts (pigments).minerals or purified metal salts (pigments).

Ruby glassRuby glass invented in 1679, using gold chlorideinvented in 1679, using gold chloride

Uranium glassUranium glass invented in 1830s, using uranium oxide.invented in 1830s, using uranium oxide.This glass glows in the dark.This glass glows in the dark.

Iridescent glass (iris glass)Iridescent glass (iris glass) made by adding metallicmade by adding metalliccompounds to the glass or by spraying the surface withcompounds to the glass or by spraying the surface withstannous chloride or lead chloride and reheating it in astannous chloride or lead chloride and reheating it in areducing atmosphere.reducing atmosphere.


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CO MP O UND S C O LO RSCO MP O UND S C O LO RSIron oxidesIron oxides greens, brownsgreens, brownsManganese oxidesManganese oxides deep amber,deep amber,

amethyst, decolorizer amethyst, decolorizer Cobalt oxideCobalt oxide deep bluedeep blueSelenium compoundsSelenium compounds redsredsGold chlorideGold chloride ruby redruby redCarbon oxidesCarbon oxides amber, brownamber, brownManganese, cobalt, ironManganese, cobalt, iron mix mix blackblack

Antimony oxides Antimony oxides whitewhiteUranium oxidesUranium oxides yellow green (glows)yellow green (glows)

Sulfur compoundsSulfur compounds amber, brownamber, brownCopper compoundsCopper compounds light blue, redlight blue, redTin compoundsTin compounds whitewhiteLead with antimonyLead with antimony yellowyellow


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Chemistry of glassChemistry of glass

Container GlassContainer Glass Main constituent is silica:Main constituent is silica:

silica sandsilica sand - - 60%60%soda ashsoda ash - - 20%20%limestonelimestone - - 15%15%aluminaalumina- -silicatesilicate - - 4%4%salt cakesalt cake - - 0.9%0.9%cullet (recycle glass) variable amountscullet (recycle glass) variable amounts


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ChemistryChemistry

FiberglassFiberglass - -Silica sand is the main constituentSilica sand is the main constituent

SodaSoda- -lime to lower workinglime to lower workingtemperaturetemperature Alumino Alumino--borosilicate glassborosilicate glassSS--glassglass high strengthhigh strengthCC--glassglass Chemical resistantChemical resistantCulletCullet


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ChemistryChemistry

Silica sandSilica sand Main constituent of glass. Basic building blockMain constituent of glass. Basic building blockhas tetrahedral shape, with silicon athas tetrahedral shape, with silicon atthe center, linked to four oxygen atoms.the center, linked to four oxygen atoms.

Rapid cooling of molten silica forms a randomRapid cooling of molten silica forms a random

organized tetrahedra, linked at corners, toorganized tetrahedra, linked at corners, toproduce an amorphous material known asproduce an amorphous material known asvitreous (glass like) silica.vitreous (glass like) silica.


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ChemistryChemistry

The high melting point and viscosity of The high melting point and viscosity of silica is reduced by adding flux (sodiumsilica is reduced by adding flux (sodiumoxide).oxide).

The cooling rate is arranged such thatThe cooling rate is arranged such thatviscosity increases and mobility of atomsviscosity increases and mobility of atomsis hindered thus preventing arrangementsis hindered thus preventing arrangementsand crystallization.and crystallization.


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Glass manufacturingGlass manufacturing

Three types of glass, potential air emissions,Three types of glass, potential air emissions,and related control devices to beand related control devices to bediscussed:discussed:

Flat glassFlat glass plate glass, architecturalplate glass, architecturalglass, automotive windscreensglass, automotive windscreens

Container glassContainer glass containers,containers,

glassware, bottlesglassware, bottlesFiberglassFiberglass insulation fiberglass,insulation fiberglass,

textile fiberglasstextile fiberglass


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Five Main ProcessesFive Main Processes

---- apply to all types of commercial glassapply to all types of commercial glassformation:formation:

Mixing, melting, forming, annealing, finishingMixing, melting, forming, annealing, finishing


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Glass processes:Glass processes:Mixing:Mixing:

Wet mixing Wet mixing - - panpan--type mixer; first drytype mixer; first dry blendblendmaterials, then wet blend.materials, then wet blend.

Batch agglomeration Batch agglomeration - - high leadhigh lead oxideoxideglass; batch particles mixed using a Muller glass; batch particles mixed using a Muller- - typetypemixer.mixer.

Both methods (1) prevent dusting, (2) control air Both methods (1) prevent dusting, (2) control air emissions, (3) ensure homogeneity, (4) increase meltingemissions, (3) ensure homogeneity, (4) increase melting

efficiency and glassefficiency and glassquality.quality.


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Glass processes:Glass processes:

Melting:Melting:Furnaces fired by natural gas or fuel oil.Furnaces fired by natural gas or fuel oil.Electric boost (auxiliary) is widely used.Electric boost (auxiliary) is widely used.

Most common furnace is theMost common furnace is thecontinuous regenerative furnace.continuous regenerative furnace.-- 45 to 272 megagrams (5045 to 272 megagrams (50 350 tpd)350 tpd)


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Glass processes:Glass processes:

FormingFormingD ifferent for each type of glass manufactured.D ifferent for each type of glass manufactured.

Flat glassFlat glass float processfloat processContainer glassContainer glass sometimes blown,sometimes blown,

but typically machine formedbut typically machine formedusing moldsusing molds

Glass fiber Glass fiber rotary spin (RS) method,rotary spin (RS) method,or flame attenuation (FA) processor flame attenuation (FA) process


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Flat glassFlat glassGlass used in windows and mirrorsGlass used in windows and mirrors

O riginally made by drawing molten glass vertically in aO riginally made by drawing molten glass vertically in aribbon from a furnace.ribbon from a furnace.

-- low quality, distortion in finished glasslow quality, distortion in finished glass

Float glass process developed in 1962.Float glass process developed in 1962.--England, Sir Alastair PilkingtonEngland, Sir Alastair Pilkington

A ribbon of glass, fed from furnace onto surface of a bath A ribbon of glass, fed from furnace onto surface of a bathof molten tin. Glass surface is heated and polished toof molten tin. Glass surface is heated and polished toremove distortion and blemishes. Glass then exits bathremove distortion and blemishes. Glass then exits bathand passes through annealing lehr to preventand passes through annealing lehr to preventnonuniform internal stresses.nonuniform internal stresses.


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Glass fiber Glass fiber Two methods of creating glass fibers:Two methods of creating glass fibers:

Rotary Spin (RS) process Rotary Spin (RS) process centrifugal force causes molten glasscentrifugal force causes molten glassto flow through holes in a spinning cylinder, creating fibers that areto flow through holes in a spinning cylinder, creating fibers that arebroken into pieces by an air stream.broken into pieces by an air stream.

Flame Attenuation (FA) Flame Attenuation (FA) molten glass flows by gravity throughmolten glass flows by gravity throughsmall orifices to create fibers that are attenuated (stretched tosmall orifices to create fibers that are attenuated (stretched tobreakage) by high velocity, hot air, and/or flame.breakage) by high velocity, hot air, and/or flame.

Glass fibers collected on a conveyor in the form of a mat.Glass fibers collected on a conveyor in the form of a mat.The mat is conveyed through curing and cooling processesThe mat is conveyed through curing and cooling processes

prior to application of backing.prior to application of backing.


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Air emissions Air emissions

Majority of air emissions originate in meltMajority of air emissions originate in meltfurnaces.furnaces.

NO

x, PM, SO

2NO

x, PM, SO

2Raw materials processingRaw materials processing PMPMContainer glass moldsContainer glass molds VO CVO C


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Air emissions Air emissions

NO xNO x -- generated in the melting furnace wheregenerated in the melting furnace whereoxygen and nitrogen are combined under highoxygen and nitrogen are combined under hightemperature. Raw materials can also containtemperature. Raw materials can also contain

nitrates that can form N O x.nitrates that can form N O x.

PMPM created by dust from raw materials blown outcreated by dust from raw materials blown outof the furnace stack. Majority is sodium sulfate.of the furnace stack. Majority is sodium sulfate.Emissions are PMEmissions are PM- -10 and PM10 and PM- -2.5.2.5.


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Air Emissions Air EmissionsS O xS O x

generated from sulfur in fuel. generated from sulfur in fuel. sulfates in raw materials. sulfates in raw materials.

As melt temperatures increase, there is an increase As melt temperatures increase, there is an increasein S O 2 emissions.in S O 2 emissions.

VO CVO C generated in forming processes where hot glass generated in forming processes where hot glasscontacts machine oil lubes.contacts machine oil lubes. binder resins (fiberglass). binder resins (fiberglass).

CO CO generated from fossil fuel combustion. generated from fossil fuel combustion. released from raw materials during melting. released from raw materials during melting.


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Control TechnologiesControl Technologies

NO x:NO x:

Three typesThree types -- combustion modificationscombustion modifications-- process modificationsprocess modifications

-- postpost--combustion modificationscombustion modifications


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Control TechnologiesControl Technologies

NO xNO xCombustion Modifications:Combustion Modifications:

low low- -NO x burnersNO x burners~ 40% reduction in N O x~ 40% reduction in N O x-- corresponding C O increasecorresponding C O increase

oxy oxy- -fuel meltingfuel melting~ 85% reduction in N O x~ 85% reduction in N O x-- reduced Natural gas usagereduced Natural gas usage-- increased production capacityincreased production capacity


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Control TechnologiesControl TechnologiesNO xNO x

oxygenoxygen- -enriched melting (oxygen burner)enriched melting (oxygen burner)-- allows more fuel to be burnedallows more fuel to be burned-- more glass producedmore glass produced-- can actually increase N O x emissionscan actually increase N O x emissions

(greater heat near the burner)(greater heat near the burner)oxygenoxygen- -enriched air staging (fuel rich andenriched air staging (fuel rich andfuel lean areas in furnace)fuel lean areas in furnace)

-- reduce N O x without increases in C Oreduce N O x without increases in C Oair stagingair staging

-- same principle as O EASsame principle as O EAS


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process modificationsprocess modifications use of extra cullet, reformulate batch use of extra cullet, reformulate batch

requires less energy,requires less energy,decrease natural gas and N O xdecrease natural gas and N O xmaintain steady production ratemaintain steady production rate

employ electric boost employ electric boostdecrease natural gas and N O xdecrease natural gas and N O xcan increase furnace temperatures andcan increase furnace temperatures andresult in S O x and PM increases.result in S O x and PM increases.


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postpost combustion modificationscombustion modifications Selective Catalytic Reduction (SCR) Selective Catalytic Reduction (SCR)

-- ammonia in presence of catalystammonia in presence of catalyst-- ~ 90% N O x reduction~ 90% N O x reduction Selective Noncatalytic Reduction Selective Noncatalytic Reduction

(SNCR)(SNCR)

-- ammonia in presence of highammonia in presence of hightemperaturetemperature-- ~ 40% N O x reduction~ 40% N O x reduction


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Control TechnologiesControl TechnologiesParticulate Matter Particulate Matter

PM reductions employing:PM reductions employing: add add- -on controlson controls

baghouses, electrostaticbaghouses, electrostaticprecipitators, and wet scrubbers.precipitators, and wet scrubbers.~ 90% reduction of PM~ 90% reduction of PM

stack temperature is a factor stack temperature is a factor

process modifications process modificationscullet use electric boost can reducecullet use electric boost can reducefurnace temperature and PMfurnace temperature and PM


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CAA regulationsCAA regulations

Six Federal Standards:Six Federal Standards:

PS D /NSRPS D /NSRNSPSNSPSNESHAPNESHAP

Seventh Standard (area source NESHAP) isSeventh Standard (area source NESHAP) isunder developmentunder development


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PS D /NSRPS D /NSR

Glass fiber processing plants:Glass fiber processing plants:40 CFR 52.21(b)(1)(i)(a)40 CFR 52.21(b)(1)(i)(a)

major sources for PS D /NSRmajor sources for PS D /NSR -- emit or emit or potential to emit 100 tons/year or morepotential to emit 100 tons/year or moreof any regulated NSR pollutant.of any regulated NSR pollutant.

Most glass fiber plants are major Most glass fiber plants are major sources and thus are subject to PS D /NSR.sources and thus are subject to PS D /NSR.


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PS D /NSRPS D /NSR

Flat or Container glass plantsFlat or Container glass plantsMajor sources for PS D /NSR if they emit or Major sources for PS D /NSR if they emit or have potential to emit 250 tons per year or have potential to emit 250 tons per year or more of any regulated NSR pollutant.more of any regulated NSR pollutant.

Most glass plants have N O x emisssionsMost glass plants have N O x emisssionsthat exceed 250 tons/year and arethat exceed 250 tons/year and aretherefore major sources. O xytherefore major sources. O xy--fuel plantsfuel plantsmay be minor due to reduced N O x.may be minor due to reduced N O x.


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New Source PerformanceNew Source PerformanceStandards (NSPS)Standards (NSPS)

40 CFR 60, subpart CC40 CFR 60, subpart CCPM standards for glass melt furnacesPM standards for glass melt furnacesconstructed or modified after 6/15/79.constructed or modified after 6/15/79.not applicable to:not applicable to: hand glass melthand glass meltfurnaces, furnaces designed to producefurnaces, furnaces designed to produceless than 5 tons of glass per day, electricless than 5 tons of glass per day, electricmelt furnaces and experimental meltmelt furnaces and experimental meltfurnaces.furnaces.


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NSPSNSPS subpart CCsubpart CC

Separate emission limits:Separate emission limits: furnaces requiring add furnaces requiring add- -on controls,on controls, furnaces that use process modifications. furnaces that use process modifications.

(less stringent)(less stringent)process modificationprocess modification any technique designed toany technique designed to

minimize emissions without use of addminimize emissions without use of add- -ononpollution controls (electric boost, cullet use, oxypollution controls (electric boost, cullet use, oxy- -

fuel melt, batch reformulation).fuel melt, batch reformulation).Performance test methods are covered inPerformance test methods are covered in40 CFR 60.296.40 CFR 60.296.


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NSPSNSPS

40 CFR subpart PPP40 CFR subpart PPPPM emission limits for rotary spin woolPM emission limits for rotary spin woolfiberglass insulation lines that commencedfiberglass insulation lines that commencedconstruction, modification, or construction, modification, or reconstruction after 2/7/84.reconstruction after 2/7/84.PM emission limit, 11 lb/ton of woolPM emission limit, 11 lb/ton of woolfiberglass is expressed in terms of thefiberglass is expressed in terms of theamount of glass pulled (60.682).amount of glass pulled (60.682).


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NSPS subpart PPPNSPS subpart PPP

NSPS identifies the use of wet scrubbersNSPS identifies the use of wet scrubbersand wet electrostatic precipitators for and wet electrostatic precipitators for reduction of PM emissions.reduction of PM emissions.

Monitoring devices and requirements areMonitoring devices and requirements arespecified in 60.683.specified in 60.683.

Recordkeeping is specified in 60.684(c).Recordkeeping is specified in 60.684(c).Reporting requirementsReporting requirements - - 60.684(d).60.684(d).Performance test requirementsPerformance test requirements - - 60.685.60.685.

National Emission Standard forNational Emission Standard for


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National Emission Standard for National Emission Standard for Inorganic Arsenic Emissions FromInorganic Arsenic Emissions From

Glass Manufacturing PlantsGlass Manufacturing Plants40 CFR 61, subpart N40 CFR 61, subpart N

rule promulgated in 1986. rule promulgated in 1986. applies to glass melt furnaces using applies to glass melt furnaces usingcommercial arsenic as a raw material.commercial arsenic as a raw material.

establishes limits and percent reduction establishes limits and percent reductionstandards for existing and new furnacesstandards for existing and new furnaces(different standards for each).(different standards for each).


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NESHAP for Inorganic ArsenicNESHAP for Inorganic Arsenicemission limitsemission limits

40 CFR 61, subpart N40 CFR 61, subpart N- -Continuous monitoring requirementsContinuous monitoring requirementsspecified in 61.163.specified in 61.163.Emissions testing requirements specifiedEmissions testing requirements specifiedin 61.163 and 61.164.in 61.163 and 61.164.

Recordkeeping requirements in 61.165Recordkeeping requirements in 61.165Reporting requirements in 61.165Reporting requirements in 61.165


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National Emission Standards forNational Emission Standards for


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National Emission Standards for National Emission Standards for Hazardous Air Pollutants HAP)Hazardous Air Pollutants HAP)

40 CFR 63, subpart NNN40 CFR 63, subpart NNN- - rule promulgated in 1999. rule promulgated in 1999. applies to existing and new glass applies to existing and new glass- -melt furnaces, rotary spinmelt furnaces, rotary spinmanufacturing (bonded), and flame attenuation manufacturingmanufacturing (bonded), and flame attenuation manufacturing(bonded pipe insulation) at(bonded pipe insulation) at

major sources.major sources. also applies to new FA manufacturing at also applies to new FA manufacturing atmajor sources producing bonded heavy densitymajor sources producing bonded heavy densityproducts.products. RS and FA manufacturing of non RS and FA manufacturing of non- -bonded products arebonded products arenot subject.not subject. Source emission limits are specified in 63.1382. Source emission limits are specified in 63.1382.

major sourcesmajor sources sources that emit at least 10 tons per year of anysources that emit at least 10 tons per year of anyone HAP or 25 tons per year of any combination of HAPs.one HAP or 25 tons per year of any combination of HAPs.


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NESHAP subpart NNNNESHAP subpart NNN

RS and FA manufacturing of nonRS and FA manufacturing of non- -bondedbondedproducts are not subject.products are not subject.

Source emissions limits are specified inSource emissions limits are specified in63.1382.63.1382.

major sourcesmajor sources sources that emit at leastsources that emit at least10 tons per year of any one HAP or 2510 tons per year of any one HAP or 25tons per year of any combination of HAPs.tons per year of any combination of HAPs.


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NESHAP subpart NNNNESHAP subpart NNN

O perating limits required IAWO perating limits required IAW63.1382(b)(163.1382(b)(1 10)10)

Monitoring requirements IAWMonitoring requirements IAW63.1383(a63.1383(a m)m)

Emissions tests requirements IAWEmissions tests requirements IAW63.138463.1384

Notification, recordkeeping, reporting IAWNotification, recordkeeping, reporting IAW63.138663.1386


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Garry Mokry Glass