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# RCRA Box 1883 Prepped byOllie Stewart



### Document

Number: 

# 98 ) ll-B-26 0 Docket Number: 

# A-90-1 9

Printed 12/3/200810:42:16

AM Sheet 98of 171P. 2 

# RADIA N CORPORATIO N 

# A-90-1 9 ll-B-26 0 Progres s O 320 0E . ChapelHil lRd./Nelso nHw )

P.O. Bo xI3000 ResearchTriangl ePark , N < •to o

February10 , 199 2 

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# L EP A AI RD < Mr Lesli e B . Evan s u!s . Environmenta l Protectio n Agency Chemical s an

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D 13 ) Researc hTriangl e Park , NC 2771 1 Dea r Les : A fh o fina l versio n o f th e memorandu mentitle d 

# ZESTS 

# s s s = £&-? sss-."* " """ ' Sincerely ,
RoyV . Oomme n Enginee r RVOrsl s Enclosur e cc : f^Mever'^P^MD-^^Wo'enclosure ) ^Uelnn e Prooert . Radian (w/ o enclosure ) Rut hMead , Radian/RT P Bennet t King , Radian/RT P Projec t Fil e 6. 1 (M-Haley )P. 3

MEMORANDU

M DATE : February10 , 199 2 TO : Lesli e B . Evan s an d Debbi e Stackhouse , EPA(MD-13 ) FROM : RoyV . Oommen , Radian SUBJECT : Limit s an d Monitoring Parameter s fo r Combustion/Scrubbing System s Use d t o Contro l Haiogenate d Proces s Ven t Stream s SUMMAR Y Th e propose d hazardou s organi c NESHAP wil l requir e combustio ncontro l o f some proces s ven t streams . Wher e haiogenate d stream s ar e combusted , scrubber s woul d b e require d t o reduc e emission s o f halogen s an d hydroge nhalides . Thi s memorandu

mpresent s technica l suppor t fo r th e emissio nlimit s an d monitoring parameter s fo r combustion/scrubbing system s use d t o contro l haiogenate d proces s ven t streams . Dat a fo r establishing th e limit s wer e gathere d fro ma surveyo f facilitie s producing ethylen e dichlorid e compounds . Tw o provision s ar e being considere d b yth e U.S . Environmenta l Protectio nAgency(EPA ) fo r inclusio ni n th e propose d standard fo r proces s ven t emissions : (1 ) a scrubbe r woul d b e require d afte r an incinerator , boiler , o r proces s heate r i f th e tota l concentratio no f haiogenate d pollutant s entering th e combustio n devic e i s greate r than 10 0 part s pe r millio n volume dry(ppmvd) , an

d (2 ) th e scrubbe r woul d b e require d t o hav e a tota l haloge n contro l efficiencyo f 9 9 percent . A n outle t concentratio n limi t o f 0. 5 milligram s pe r drystandard cubi c mete r (mg/dscm ) mayb e provide d a s an alternativ e t o th e percen t reductio nfo r stream s wher e 9 9 percen t contro l woul d resul t i n outle t level s belo wth e detectio nlimi t an d therefor e b e unmeasurable . Thi s memorandu mprovide s technica l informatio n supporting thes e provisions .

monpaxhtm04(ls ) 1P. 4

Th e propose d EPATes t Metho d 26 Ai s recommende d t o measur e th e concentration s exiting th e scrubbe r an d t o confir

mth e contro l efficiencyo f th e scrubbe r during th e require d initia l performanc e test . T o ensur e th e scrubbe r continue s t o mee t th e standard s afte r th e performanc e test , th e p H o f th e effluen t scrubbe r solutio n fro mth e las t scrubbe r stag e an d th e liquid-to-ga s rati o (L/G ) woul d b e monitored . Furthe r elaboratio n i s presente d i n th e following sections : Introductio n(1.0) , Dat a Collectio n(2.0) , Scrubbe r Parameter s fo r Surveye d Facilitie s (3.0) , Potentia l Provision s fo r th e Standard (4.0) , Measuremen t Technique s (5.0) , Scrubbe r Monitoring Parameter s (6.0) , an d Reference s (7.0) . 1. 0 INTRODUCTIO

N A s par t o f th e Hazardou s Organi c NESHAP (HON ) development , th e EPAha s identifie d combustio na s a viabl e metho d fo r controlling emission s o f organi c pollutants . However , th e combustio n o f haiogenate d organi c compound s (i.e. , organi c compound s containing chlorine , fluorine , etc. ) mayresul t i nth e formatio n an

d emissio no f specie s suc ha s hydroge n chlorid e (HCl) , hydroge n fluorid e (HF) , an d chlorin e (Cl 2 ) whic har e als o o nth e lis t o f 19 0 hazardou s ai r pollutant s unde r Titl e II I o f th e Clea n Ai r Ac t Amendments . T o ensur e tha t combustio no f haiogenate d pollutant s wil l no t adversel yimpac t th e environment , a secondarycontro l devic e ( a scrubber ) i s neede d t o reduc e emission s generate d b yth e primarycontro l devic e (incinerator , boiler , o r proces s heater) . 2. 0 DAT

ACOLLECTION Asurveyo f chemica l facilitie s producing haiogenate d compound s wa s conducte d t o identif yth e mos t commo ntype s o f secondarycontro l device s currentl yi n use , an d th e resulting aci d ga s emission s fro mthem . I n orde r t o mak e th e survey manageable , th e scop e wa s limite d t o chemica l facilitie s producing ethylen e dichlorid e (EDC) . Ethylen e dichlorid e wa s

monparhtm

O 4(Is ) 2P. 5

chose nbecaus e i t i s produce d i nlarg e quantities , an d facilitie s producing ED C woul d b e expecte d t o hav e larg e aci d ga s release s and/o r secondarypollutio ncontro l device s i n place . Atota l o f fiv e companie s (BFGoodrich , Borden , Dow , Occidental , an d PPG ) i n eigh t location s wer e surveyed . Four o f th e eigh t plan t site s produc e viny l chloride , an d on e produce s polyviny l chloride , a s wel l a s EDC . Tabl e 1 present s th e EDC productio n capacitie s o f th e eigh t facilities , thei r primaryan d secondaryai r pollutio n contro l devices , an

d th e haiogenate d pollutant s emitte d fro mthei r primarycontro l device . Seve n o f th e eigh t facilitie s reporte d therma l incineratio n a s th e primarycontro l device . Th e exceptio n i s Do wChemical' s Freepor t plant , whic hreporte d tha t proces s ven t emission s wer e sen t t o a flare . Quantitativ e dat a o nemission s an

d contro l efficiencie s wer e no t supplie d b ythi s facility . Chlorin e ga s an d HC l ar e th e mos t commo nhaiogenate d pollutant s emitte d fro mth e incinerator s a t th e seve nfacilities . Althoughonl yon e o f th e eigh t facilitie s reporte d using flare s a s th e primarycontro l device , bot hth e Texa s Ai r Contro l Board (TACB ) " an

d th e Louisiana Ai r Contro l Board (LACB) 1 7 indicate d tha t flare s ar e no t prohibite d fro mbeing use d t o contro l haiogenate d ga s stream s i n thei r States . However , th e TAC B an d LAC B als o indicate d tha t flare s ar e no t normall yused , an d ar e usuall ydiscourage d fro mbeing use d fo r thi s purpose . Neithe r th e TAC B o r LAC B impos e concentratio nlimit s o n haiogenate d compound s entering flares , s o flar e applicabilit yi s determine d o n a case-by-cas e basi s using dispersio nmodeling . 3. 0 SCRUBBE RPARAMETER S FORSURVEYE D FACILITIE S Th e seve nfacilitie s reporting incineratio n a s th e primary contro l devic e als o reporte d we t scrubber s a s th e secondary contro l device . Tabl e 1 present s some o f th e characteristic s o f th e scrubbers . Al l o f th e scrubber s us e packe d columns ; si xus e causti c a s th e scrubbing solven t an d on e use s water .

monparhtmOA(Is )Tabl e 1 . Existin g Control s a t Ethylen e Dichlorid e Facilities 1

PLAN T COD E COMPANY LOCATIO N ED C PRODUCTIO N CAPACIT Y (M MKg/yr ) PRIMARY

CONTRO L DEVIC E COMPOUND S

EXITIN G PRIMAR Y DEVIC E SECONDAR Y

CONTRO L COLUM N DEVIC E TYP E SCRUBBIN G OPERATIO NSOLVEN T A 2 ' 3 BFGOODRIC H B 3 ' 4 BORDE N

C DO W

D 3, 5 DO W

E 3 ' 5 DO W F 2 OCCIDENTA L GOCCIDENTA L H PP G LAPORT E T X GEISMARL A

FREEPOR T T X

OYSTE RCREE K T X PLAQUEMIN E L A CORPU S CHRIST I T X CONVEN T L A LAK E CHARLE S L A 72 0 INCINERATO RClj , HC l 33 9 INCINERATO RCl 2 , HC l Trac e Amount s o f Othe r Halogen s 72 7 FLAR E Trac e Amount s o f Haiogenate d Compound s 50 0 INCINERATO RCl 2 , HC l Trac e Amount s o f Othe r Halogen s 77 3 INCINERATO RCl 2 , HC l 36 4 364 122 7 INCINERATO RCl 2 , HC l

INCINERATO RCl 2 , HC l INCINERATO RCl 2 , HC l SCRUBBE RPACKE D SCRUBBE RPACKE D RECYCL E CAUSTI C RECYCL E WATE R

NON E ND ND N D

SCRUBBE RPACKE D RECYCL E CAUSTI C

SCRUBBE RPACKE D SCRUBBE RPACKE D SCRUBBE RPACKE D SCRUBBE RPACKE D ONC E CAUSTI C THROUG H RECYCL E CAUSTI C RECYCL E CAUSTI C RECYCL E CAUSTI C ND = n o dat a 1 Reference s 1-1 3 2 plant s tha t d o no t produc e HC l 3 plant s tha t als o produc e viny l chlorid e (VC ) 4 plant s tha t als o produc e polyviny l chlorid e (PVC ) 5 wast e hea t boiler sP. 7

Tabl e 2 present s th e reporte d informatio no nth e performanc e o f eac hscrubber , including : aci d ga s (HC l an d Cl 2 ) outle t concentrations , tes t method s use d fo r determining aci d ga s concentrations , HC l design remova l efficiency , p H o f scrubbing liquid , exiting temperatur e o f th e effluen t gas , an d th e maximu

m flowrat e o f effluen t gas . Fo r th e surveye d facilities , Tabl e 2 indicate s onl ytw o pollutants , HC l an d CI2 , wer e reporte d exiting th e scrubber . Figur e 1 present s th e HC l an d CI 2 concentration s i nth e effluen t ga s fro mth e scrubbers , b

yfacility . Hydroge n chlorid e emission s range d fro m0.9 3 ppmv

d t o 7 2 ppmvd , wit han averag e valu e o f 3 3 ppmvd . Chlorin e emissio nlevel s range d fro m 0.7 5 ppmv

d t o 2 6 ppmvd , wit han averag e valu e o f 1 1 ppmvd . Al l emission s dat a ar e correcte d t o 3 percen t oxyge n basi s t o correlat e wit hth e propose d HONstandards . A s Tabl e 2 indicates , 8 o f th e 1 0 scrubber s hav e HC l design remova l efficiencie s equa l t o o r abov e 9 9 percent . Scrubber s i n facilitie s E (Dow ) an d G(Occidental ) reporte d designremova l efficiencie s o f 9 8 an d 9 7 percent , respectively . Al l bu t on e we t scrubbe r use s causti c a s th e solvent , wit hpH' s ranging fro m 7. 5 t o 10.5 . Th e exceptio n i s Facilit yB (Borden) , whic huse s wate r a s th e scrubbing liquid . Al l bu t on e o f th e outle t ga s temperature s wer e betwee n 10 0 an d 18 8 degree s Fahrenheit . Th e exceptio n i s Facilit yG(Occidental) , whic hreporte d a valu e o f 38 9 degree s Fahrenheit . However , thi s valu e i s suspect , a s i t i s abov e th e boiling poin t o f water . Effluen t ga s flowrate s rang e fro m1,97 7 dscf m

t o 33,70 3 dscfm . 4. 0 POTENTIAL PROVISION S FORTH E STANDARD Tw o provision s fo r combustor/scrubbe r system s ar e being considere d b

yth e EPAfo r inclusio n i n th e HO Nstandard : (1 ) scrubbing i s require d i f th e inle t concentratio nt o th e incinerator , boiler , o r proces s heate r i s greate r tha n 10 0 ppmv d o f haiogenate d organi c compounds , an d (2 ) scrubber s mus t hav e a tota l haloge nan

d hydroge n halid e contro l efficiencyo f 9 9 percen t o n a mola r basis .

monparhtm04(ls ) 5. • .

COD E

A B C D

o > E F

G H

* = N D = COMPAN Y BFGOODRIC H BORDE N DO W DO W

DO W OCCIDENTA L

OCCIDENTA L PP G Typica l flo w = N o Dat a Tabl e 2 .

SCRUBBE R NUMBE R
A- l B- l C- l D- 1 D- 2 D- 3 E- 1 F- l F- 2 G- l H- l H- 2 Scrubbe r Characteri s

HC l DESIG N REMOVA L EFFICIENC Y (% ) 99. 9 99. 0 N D 99. 9 N D 99.^ 0 98. 0 99. 7 99. 7 97. 1 99. 1 99. 9 SOLVEN T

P H 8. 5 6.5-7. 0 N D 9. 5 9. 0 10. 5 8. 5 8. 5 8. 5 7. 5 8. 5 9. 0 >tic s c

S C

GA S EXI T TEM P (F ) 14 2 14 0 N D 15 1 15 0 18 8 10 0 17 8 17 9 38 9 13 9 10 9 -

>f th e Surveye d Facilitie s

:RUBBE RDAT A REPORTE D MAX . CONCENTRATION S GA S I NTH E EXI T GA S FLO W(ppmvd, @ 3 % 0 2 ) RAT E (DSCFM ) HC l Cl 2 3370 3 3069 8 N D 619 5 460 1 382 3 278 8 193 5 197 7 N D 1265 3 882 0 * *

* * 0.9 3 1 3 N D 6 3 3 4 2 7 1 2 6 5 1 7 2 6 2 0.7 5

2 6 N D 1 7 1 2 7 N D N D N D N D 1 1 -

TES T METHO D TAC B #1 0 N D N D EP A005 0 EP A005 0 EP A005 0 EP A005 0 EP A2 6 EP A2 6 EP A2 6 N D N D -

•

# Figur e 1
. HC l an d CI 2 Emission s Outle tFro m Scrubbe r

C N O r o

> E 

### a a c o o l
_ -•- ' c <u c o 

### o

D HC l Emission s + CI 2 Emission sP.1 0

N o informatio nwa s availabl e fro mM C 1 2 incinerator/scrubbe r installation s o nth e amoun t o f haiogenate d compoun d i n th e incinerato r inle t o r th e amoun t o f HC l an d CI 2 i nth e incinerato r outlet . Th e incinerato r inle t haiogenate d organi c compoun d level s wer e therefor e calculate d base d o n th e combustio no f a mode l haiogenate d organi c molecul e an d th e reporte d scrubbe r outle t concentration s presente d i nTabl e 2 . Th e mode l haiogenate d compoun d wa s develope d b

yth e EP

Ai n a previou s 1 8 study . Th e concentratio no f th e mode l compoun d a t th e entranc e t o th e incinerato r wa s estimate d using stoichiometri c balance s an d assuming th e scrubbe r ha s a contro l efficiencyo f 9 9 percen t fo r HC l an

d 9 5 percen t fo r CI 2 (se e Appendi xA. 1 fo r sampl e calculations) . Tabl e 3 present s th e calculate d inle t haiogenate d organi c compoun d concentration s fo r th e facilitie s i n th e database . Th e minimu minle t concentratio n fo r th e incinerator/scrubbe r contro l system s wa s determine d t o b e abou t 13 0 ppmv d fo r a scrubbe r onl y reporting HC l outle t emissio nlevels , an d abou t 16 0 ppmv

d fo r a scrubbe r reporting bot hHC l an d CI 2 emissions . Thes e calculation s includ e simplifiying assumption s an d ar e viewe d a s accurat e t o on e significan t figure . Avalu e o f roughl y10 0 ppmv d coul d b e include d i n th e regulation s a s th e minimu mconcentratio n o f tota l haiogenate d organi c compound s entering anincinerator , boiler , o r proces s heate r tha t woul d requir e subsequen t scrubbing . Thi s approac hwa s take nbecaus e th e collecte d dat a suppor t 9 9 percen t remova l fo r combustor/scrubbe r system s wit h scrubbe r outle t concentration s onl ywithi n th e rang e covere d b y th e surveydata , an d applicabilit yan

d performanc e o f scrubber s t o stream s wit houtle t haloge nlevel s belo wthi s rang e i s uncertain . Th e regulatio n woul d als o stat e th e stream s wit h haiogenate d organi c concentration s abov e 10 0 ppmv d canno t b e introduce d t o a flare .

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Tabl e 3 . Mode l Haiogenate d Compoun d Concentration s fo r Surveye d Facilitie s

COD E A B C D

E F

G H COMPANY

BFGOODRIC H BORDE N DO W DO W

DO W OCCIDENTA L

OCCIDENTA L PP G SCRUBBE R

NUMBE R A- l B- l C- l D- 1 D- 2 D- 3 E- 1 F- l F- 2 G- l H- l H- 2 CALCULATE D

INCINERATO R INLE T CONCENTRATIO N (ppmvd ) 16 4 3,27 2 N D 10,23 8 46 5 7,61 2 10,41 5 * 3,63 9 * 68 5 * 13 2 * 10,63 7 9,07 1 N D = n o dat a * = value s fro

m HC l concentratio n onl ya s chlorin e wa s no t provided .P.1 2

Eigh t o f th e te n facilitie s i nth e databas e reporte d a nHC l designremova l efficiencyo f a t leas t 9 9 percen t wit hsome a s higha s 99. 9 percent . Th e remaining tw o reporte d 9 7 an d 9 8 percen t efficiencies . Asurveyo f ga s absorbe r vendor s als o indicate d tha t 9 9 percen t contro l o f HCl , HF , bromin e (Br 2 ) , an d

« * 19-2 0 Cl 2 i n ga s stream s i s achievable . Base d o nthi s information , 9 9 percen t overal l contro l o f halogen s an d hydroge n halide s fro m scrubber s woul d b e achievabl e an d coul d b e include d a s a provisio n t o th e propose d standard . Haloge nremova l mayb e slightl ylowe r tha nhydroge nhalides , bu t haloge nconcentration s a t scrubbe r inlet s an d outlet s ar e generall yexpecte d t o b e lowe r tha nfo r hydroge n halides . 5. 0 MEASUREMENT TECHNIQUE S I norde r t o demonstrat e 9 9 percen t control , outle t concentration s fro

mth e scrubbe r a s lowa s 0. 8 ppmv d maynee d t o b e measured . (Thi s valu e wa s reporte d fo r Cl 2 a t on e o f th e facilitie s surveyed) . Amemorandu mfro m TerryHarriso no f th e EPA , date d Augus t 9 , 199l, 2 1 indicate d tha t EPAMetho d 2 6 an d propose d Metho d 26 Aar e applicabl e fo r measurement s a t thes e levels . Bot hmethod s can b e use d t o measur e th e following halogen s an

d hydroge n halides : HCl , HF , hydroge nbromid e (HBr) , Cl 2 , an d Br 2 . Metho d 2 6 i s use d fo r non-isokineti c sampling . Metho d 26 Ai s applicabl e fo r isokineti c sampling . I t i s expecte d tha t some o f th e halogen s an d hydroge n halide s exiting th e scrubbe r wil l b e entraine d i nmoistur e droplets . Therefore , isokineti c sampling using Metho d 26 Ai s th e recommende d measuremen t method . However , Metho d 26 Atend s t o showa bia s fo r lowe r concentrations . Th e metho d i s currentl yunde r revie wb y th e EPAt o resolv e thes e issues . Th e lowe r analytica l detectio n limi t o f Metho d 26 Ai s approximatel y0.0 8 mg/dscm (se e calculation s i nAttachmen t A.2) . Astandard facto r o f 5 time s th e detectio n limi t result s i nan alternat e lowe r cutof f o f approximatel y0. 5 mg/dscm . I f a facilit yca n demonstrat e anoutle t concentratio n belo w monparhtm O 4 (Is ) 1 0P.1 3

0. 5 mg/dscm

fo r eac hhaloge n o r hydroge nhalid e specie s present , th e propose d regulatio n coul d specif ytha t th e facilit ywoul d b e considere d t o b e i n complianc e an d th e inle t concentratio nwoul d no t hav e t o b e measure d an d percen t reductio nwoul d no t nee d t o b e calculated . Thi s alternat e concentratio n leve l i s neede d becaus e facilitie s canno t reliabl ymeasur e concentration s belo w 0. 5 mg/dscm . 6. 0 SCRUBBE RMONITORIN GPARAMETER S AN

D LIMIT S Th e appropriat e monitoring parameter s t o ensur e scrubbe r complianc e wit hth e standard ar e th e p H o f th e effluen t fro mth e las t scrubbe r stage , an d th e liquid-to-ga s (L/G ) ratio . Th e p H o f th e effluen t fro mth e las t scrubbe r stag e i s an indicato r o f it s acidit y(i.e. , amoun t o f aci d ga s dissolved) . I f th e p H i s lowe r tha n normal , th e scrubbe r i s unlikel yt o b e removing sufficien t aci d i n th e ga s t o operat e a t th e specifie d efficiencyo r t o mee t th e propose d regulation . Th e p H valu e necessaryt o achiev e performanc e requirement s can b e determine d b yoperating a t th e maximu mhaloge n mas s flowrat e during th e initia l performanc e test . During subsequen t operation , th e averag e p H shoul d b e maintaine d a t a leve l no t les s tha n1 p H uni t belo wth e valu e measure d during th e performanc e test . Th e averag e operating p H value s woul d b e determine d during 3-hour measuremen t periods . Thi s 3-hour averaging perio d i s consisten t wit hth e averaging perio d use d fo r al l o f th e othe r proces s vent , combustion , an

d recoverydevic e monitoring parameter s i nth e propose d HONregulation . Th e p H canb e monitore d using a monitoring devic e wit ha continuou s recorder , whic har e readil y availabl e fro

m vendors . Monitoring th e p H alon e wil l no t adequatel yindicat e whethe r th e scrubbe r i s operating properl yt o mee t th e propose d regulation . Fo r example , a p H chang e mayals o indicat e th e ga s flowrat e i s smalle r o r large r tha na t norma l operating conditions . Th e p H coul d b e withi nth e propose d limits , bu t th e aci d ga s contro l efficiencyo f th e scrubbe r coul d b e reduce d i f th e liquid-to-ga s contac t withi n th e scrubbe r i s belo wnorma l levels . Therefore , th e L/ Grati o shoul d als o b e monitored . Decrease d L/ Gvalue s indicat e a smalle r liqui d o r large r ga s flow monparhtm

O 4 (Is ) 1 1P.1 4

rate , wit ha resultan t declin e i nperformance . A t maximu m operating load (i.e. , whe n Gi s large) , th e L/ Grati o tend s towar d a minimu

m value . Th e minimu mL/ Grati o necessaryt o achiev e th e performanc e requirement s shoul d b e se t a s a limiting parameter . Th e L/ Gvalu e woul d b e determine d during th e performanc e tes t whil e th e proces s uni t i s operating a t minimu m liqui d flowan

d maximu

m ga s flowrate s an

d achieving 9 9 percen t removal . Th e scrubbe r woul d the nb e require d t o monito r L/ Gan d repor t an

y3-hour perio d whe nth e averag e L/ Gi s mor e tha n 5 percen t belo wth e averag e valu e measure d during th e performanc e test . Th e liqui d an d ga s flowrate s can b e measure d using continuou s flowmeter s whic har e availabl e fro m vendors . Th e flowmeter s woul d b e installe d a t th e ga s an d liqui d inlet s t o th e scrubber .

mon p arhtro O 4(Is ) 1 2P.1 5

7. 0 REFERENCE S 1 . Questionnair e respons e fro mGustafson , David , Do wChemical , Midland , MI , t o Oommen , R.V. , Radian . May22 , 1991 . Faxo f respons e t o question s concerning scrubbe r exi t concentrations . 2 . Questionnair e respons e fro mGustafson , David , Do wChemical , Midland , M I t o Oommen , R.V. , Radian . May1 , 1991 . Faxo f questionnair e o n parameter s o f scrubbe r exi t gas . 3 . Questionnair e respons e fro mGustafson , David , Do wChemical , Midland , MI , t o Oommen , R.V. , Radian . Apri l 26 , 1991 . Faxo f respons e t o question s concerning parameter s o f th e scrubbe r exi t gas . 4 . Questionnair e respons e fro m Arnold , Sherrie , Do wChemical , Midland , M I t o Oommen , R.V. , Radian . Marc h26 , 1991 . Faxo f questionnaire.o n contro l technologie s use d t o trea t proces s ven t streams . 5 . Questionnair e respons e fro mEmery , Elizabeth , Borde n Chemical s an

d Plastics , Geismar , LA , t o Oommen , R.V. , Radian . May2 , 1991 . Faxo f questionnair e o nparameter s o f scrubbe r exi t gas . 6 . Questionnair e respons e fro mEmery , Elizabeth , Borde n Chemical s an

d Plastics , Geismer , LA , t o Oommen , R.V. , Radian . Apri l 1 , 1991 . Faxo f questionnair e o ncontro l technologie s use d t o trea t proces s ven t streams . 7 . Questionnair e respons e fromHinson , David , B F Goodric h Intermediates , L a Porte , TX , t o Oommen , R.V. , Radian . Apri l 30 , 1991 . Faxo f incinerato r an d stac k data . 8 . Questionnair e respons e fromHinson , David , B F Goodric h Intermediates , L a Porte , TXt o Oommen , R.V. , Radian . Apri l 2 , 1991 . Faxo f questionnair e o ncontro l technologie s use d t o trea t proces s ven t streams . 9 . Telecon . Oommen , R.V. , Radia n wit hLiggio , Esther , PPG , Environmenta l Engineer , May10 , 1991 . Teleco n abou t scrubbe r exi t ga s parameters . 10 . Questionnair e respons e fro mLiggio , Esther , PP GChemicals , Lak e Charles , LA , t o Oommen , R.V. , Radian , May8 , 1991 . Fax o f questionnair e o ncontro l technologie s use d t o trea t proces s ven t emissions . 11 . Lette r fromEwen , Kelly , Occidenta l Chemica l Corporation , Convent , LA , t o Oommen , R.V. , Radian . Apri l 24 , 1991 , Lette r concerning parameter s o f scrubbe r exi t gas .

monparhtmOA(Is ) 1 3P.1 6

12 . Telecon . Wilson , Jim , Occidenta l Chemica l Co. , Corpu s Christi , TX , wit hOommen , R.V. , Radian , Apri l 22 , 1991 , Teleco n o f respons e t o question s abou t scrubbe r exi t ga s parameters . 13 . Questionnair e respons e fro m Takacs , Lazlo , Occidenta l Chemica l Center , Niagar a Falls , NY , t o Oommen , R.V. , Radian . Marc h26 , 1991 . Faxo f questionnair e o ncontro l technologie s use d t o trea t proces s ven t streams . 14 . Telecon . Oommen , R.V. , Radian , wit hHome , Karen , Texa s Ai r Contro l Board . May15 , 1991 . Teleco n o nflar e use . 15 . Telecon . Oommen , R.V. , Radian , wit hOlsen , Karen , Texa s Ai r Contro l Board . Apri l 25 , 1991 . Teleco n o nflar e use . 16 . Telecon . Disorbo , S. , Radian , wit hSaitas , J. , Texa s Ai r Contro l Board . Apri l 26 , 1991 . Teleco no nflar e use . 17 . Telecon . Oommen , R.V. , Radian , wit hDavis , B. , Louisiana Ai r Contro l Board . May17 , 1991 . Teleco no nflar e use . 18 . Organi c Chemica l Manufacturing Volume 4 : Combustio nContro l Devices , EPA-450/3-80-026 . Offic e o f Ai r Qualit yPlanning an d Standards , U.S . Environmenta l Protectio n Agency . 19 . Airpol , Inc. , Peterboro , NJ , Bulleti nPT/89-5M , 1991 . 20 . Midwes t Ai r Products , Co . Inc. , Onosso , MI , Produc t Catalog , 1991 . 21 . Memorandu

m fro mHarrison , Terry , EMB/EPAt o Oommen , R.V. . Radian . Augus t 9 , 1991 , Faxo f applicabl e tes t method s fo r measuring halogen s fro mscrubbers .

monparhtmO * (Is ) 1 4P.1 7

APPENDI XA A. 1 SAMPL E CALCULATIONFORMODE L HALOGENATE D COMPOUN D CONCENTRATION S AT TH E INCINERATORINLE T A. 2 CALCULATIO

NO F METHO D 26 ADETECTIO NLIMI T

monparhtmOA(Is )P.1 8

A. 1 SAMPL E CALCULATIO NP.1 9

A. 1 SAMPL E CALCULATIO NO F TH E MODE L HALOGENATE D COMPOUN D CONCENTRATIONAT TH E INCINERATORINLE T PURPOSE : Th e objectiv e o f thi s sectio ni s t o presen t exampl e

calculation s fo r estimating th e haiogenate d organi c compound concentratio nentering an incinerato r tha t correlate s t o specifi c scrubbe r outle t HC l an d CI 2 concentrations . FLOWDIAGRAM : Th e basi c bloc k flowdiagra m o f th e pollutio n contro l systemi s represente d as :

Wast e Strea

m(W ) Incinerato r Effluen t Strea m1 (Ei ) Scrubbe r Effluen t Strea m2 (E 2 ) >

Th e scrubbe r i s assume d t o b e 9 9 percen t efficien t fo r HC l control , an

d 9 5 percen t efficien t fo r CI 2 contro l base d o n th e informatio ncollecte d an d ga s absorbe r vendo r surveys . PROCEDURE : Sinc e th e onl yinformatio nknowni s th e HC l an d CI 2 scrubbe r outle t concentrations , th e following procedure s wil l b e used . 1 . Frompollutan t concentration s i nE 2 an d remova l efficiencies , pollutan t concentration s i nE i wil l b e calculated . 2 . Frompollutan t concentration s i nE ^ an d stoichiometri c balances , th e haiogenate d organi c compound concentratio no f Wwil l b e calculated , taking int o accoun t dilutio n ai r requirements .

sampcalchtm04(Is ) A.1- 1P.2 0

A.1. 1 CALCULATIONO F MODE L HALOGENATE D ORGANI C COMPOUN D Apreviou s EPAprojec t establishe d a mode l haiogenate d VO C molecul e wit hth e following composition: 3 b yweigh t percen t 34.3 % Carbo n 4.7 % Hydroge n 60.6 % Chlorin e T o conver t t o moles , assume 10 0 l bbasis :

Carbon : 34. 3 l b• l bmole= 2.8 6 l bmol e

12.0 1 l b Hydrogen : 4. 7 l b l bmol e 1.00 8 l b 4.6 6 l bmole s

Chlorine : 6 0. 6 l b l bmol e 35. 5 l b 1.7 1 l bmole s

c 2.8 6 H 4.6 6 cl 1.7 1

a Organi c Chemica l Manufacturing Volum e 4 : Combustio n Contro l Devices , EPA-450/3-80-026 . Offic e o f Ai r Qualit y Planning an

d Standards , U.S . Environmenta l Protectio nAgency .
s ampc alchtm

O4(Is ) A . 1- 2P.2 1

A.1. 2 CALCULATIONO F HALOGENATE D ORGANI C COMPOUN D CONCENTRATION I NWAST E STREA

M(W ) Exampl e Case : Inle t t o incinerato r = 0 % oxyge n i nwast e strea m (W ) Outle t fro

mscrubbe r =3 % oxyge ni n Effluen t (dr ybasis ) strea

m2 (E2 ) Anexampl e calculatio n wil l b e presente d using scrubbe r outle t dat a fromth e B.F . Goodric hfacilit y(se e Tabl e 2 i nth e memorandum) . HC l concentratio n= .9 3 ppmv d CI 2 concentratio n= .7 5 ppmv d Th e concentratio n value s ar e converte d t o mol e % value s using th e equation : mol e percen t = (100 ) xppmv d IO 6 Therefore : HC l mol e percen t = (100 ) ( .93. = 9. 3 xIO - 5 IO 6 Cl 2 mol e percen t = (100 ) ( .75. = 7. 5 x10~ 5 IO 6 Par t l : Calculatio no f Effluen t Strea m 1 (E] J Th e drycompositio n o f E 2 i s comprise d o f HCl , CI2 , O2 , N2 , CO2 , an d some iner t compound . Assume E 2 = 10 0 l bmol e drybasis . I f strea

m E 2 contain s 3 % O 2 the n i t woul d hav e 3 lb-mole s o f O 2 (10 0 lb-mole s x.03 ) i n it . Th e strea mentering th e scrubbe r i s calculate d fromth e following balance .

sampcal_htm04(ls ) A. 1 — 3P.2 2

Assumin g 9 9 % efficienc yfo r HCl :

X E 2 E l i _efficienc y

10 0 HCl , HC l

E2_ 1 - 9 9 10 0 9. 3 x1 0

.0 1 - 5 = .009 3 l bmole s

Wher e X E 2 i s th e concentratio no f a haiogenate d specie s i nstrea m ^ 2 an d Xg - i s th e concentratio no f th e haiogenate d specie s i nEj_. Assumin g 9 5 % efficienc yfo r CI2 :

CI . CI
- •E ? 7. 5 X1 0 - 5

1 - 9 5 10 0 0 5 001 5 l bmole s

E i + z HC l = .009 3 l bmole s CI 2 = .001 5 l bmole s Inert s = wl bmole s — > CO 2 = xl bmole s N 2 = yl bmole s °- 2 = 3 l bmole s wate r = z lb-mole s Scrubbe r 99 % HC l 95 % Cl 2 E 2 + z

HC l = 9. 3 x10" 5 l bmole s Cl 2 = 7. 5 xIO" 5 l bmole s

- > Inert s = wl bmole s CO 2 = xl bmole s N 2 = YI* 3 mole s 0 2 = 3 l bmole s wate r = z l bmole s Assum e CO2 , N2 , an d O 2 d o no t chang e acros s th e scrubber .

sampcalchtm04(Is ) A . 1- 4Exampl e Case : (Continued )

Par t 2 : Calculatio no f haiogenate d organi c compound concentratio n i n wast e strea m(W ) Th e following diagra mpresent s th e flowstream s entering an d exiting th e incinerator :

Fue l (CH4 ) Theoretica l ai r W

c 2.8 6 H 4.6 6 cl 1.7 1 + Inert s (Assum

e N2 ) Incinerato r Ex+ Z HC l = .009 3 l bmole s Cl 2 = .001 5 l bmole s Inert s = wl bmole s CO 2 = xl bmole s t N 2 = yl bmole s Dilutio nAi r O 2 = 3 l bmole s Wate r = z l bmole s Th e concentratio n o f th e haiogenate d molecul e entering th e incinerato r i n strea mWwil l b e calculate d fro mth e stoichiometry o f th e combustio no f th e haiogenate d molecul e an d fuel , an

d th e subsequen t enthalpybalance . (1 ) Stoichiometryo f Haiogenate d Organi c Compoun d Combustio n (Assum e complet e combustion ) .007 2 C 2 .8 6 H 4.6 6 cl 1.7 1 _ > - 0 1 2 H 2 ° -009 3 HC l + .001 5 Cl 2 + + .02 7 0 2 .02 1 C0 2 Th e theoretica l O2 , theoretica l air , nitroge n i n theoretica l air , dilutio n air , an

d moistur e i ntheoretica l ai r an d dilutio n ai r nee d t o b e calculated . 1 . Theoretica l O 2 neede d = [(mole s H2O ) (Oxygenatom s i n H2O ) + (Mole s CO2 ) (Oxygen atom s i nCO2)]/Oxyge n atom s i nO 2

= [(.012 ) + 2(0.021)]/ 2 = 0.02 7 l bmole s 0 2 2 . Theoretica l ai r = Theoretica l 02/Fractio n o f O 2 i nAi r

= [0.02 7 mole s 0 2 /.21 ] = .12 9 l bmole s ai r 3 . Nitroge n i ntheoretica l ai r

= (Theoretica l air ) (fraction o f N 2 i nair )

= (.129 ) (.79 ) = .10 2 l bmole s N 2 4 . Dilutio nai r require d = Exces s 02/Fractio no f O 2 i nai r

= [ 3 l bmole s exces s O2/.2I ] = 14. 3 l bmole s sa__pcalchtm04(ls ) A.l~ 5P.2 4

5 . Moistur e i ntheoretica l ai r (assum e ai r i s saturate d a t 77°F )

= .01 3 lb s moisture/l bdr yair. a Moistur e = .12 9 l bmole s ai r * (29. 1 l bair/l bmol e air) *

.01 3 l bwater/l bdr yai r * (l bmol e water/1 8 lbs )

= .00 3 l bmole s wate r 6 . Moistur e i ndilutio n ai r (assum e ai r i s saturate d a t 77°F )

= .01 3 lb s moisture/l bdr yair . Moistur e = 14. 3 l bmole s ai r * (29. 1 l bair/l bmol e air) *

.01 3 l bwater/l bdr yai r * (l bmol e water/1 8 lbs )

= . 3 l bmole s wate r (2 ) Stoichiometr yo f Fue l Combustio n (Assum e methan e i s fuel ) Se e ste p (1 ) fo r formula s used .

a CH 4 + 2 a O 2 — > a CO 2 + 2 a H2 O wher e a = mole s o f CH 4 1 . Theoretica l O 2 neede d = 2 a l bmole s 2 . Theoretica l Ai r = 2a/.2 1 = 9.52 a l bmole s 3 . Nitroge n i n theoretica l ai r = 7.5 2 a l bmole s 4 . Moistur e i ntheoretica l ai r (assum e ai r i s saturate d a t 77°F )

= .01 3 lb s moisture/l bdr yair . Moistur e = 9.5 2 a l bmole s ai r * (29. 1 l bair/l bmol e air) *

.01 3 l bwater/l bdr yai r * (l bmol e water/1 8 lbs )

= . 2 a l bmole s wate r (3 ) Enthalp yBalanc e A n enthalp ybalanc e i s require d t o estimat e th e valu e o f o c

• Assum e hea t releas e fro mth e combustio no f th e mode l compoun d i s insignificant . • Incinerato r operatin g temperatur e = 2,000° F (base d o nHO N incinerato r parameters ) Referenc e temperatur e = 77° F Hea t o f combustio no f CH 4 = Hea t gai nbyth e product s o f combustio n

a Felder , R.M . an d Rousseau , R.W . Elementar yPrinciple s o f Chemica l Processes . Secon d Edition . 1986 . Joh nWile yan d Sons . sampcalchtn.04(ls ) A. 1 — 6P.2 5

« H CH4 = (MC p AT)co 2 + (MCpAT) n o + (MCpAT) N 2 theoretica l

(MC AT) N 2 exces s ai r (MC p AT)o 2 exces s ai r + (MCpAT)inert s

where : H CH 4 = Hea t o f combustio n o f methan e = 23,87 5 Btu/lb a MWCH4 = 1 6 lb/l bmol e M= mole s o f eac hcompoun d liste d i nincinerato r exhaus t fro m combustin g CH 4 an d mode l VO C molecule . A T = Incinerato r temperatur e minu s referenc e temperatur e (2000-77 )

c p = Hea t capacit yo f th e product s o f combustio nliste d Hea t Capacit yo f Compounds 0 Pollutan t Hea t Capacit yCoefficient s C p abe d (Btu/l bmole°F) c



### co 2 H 2 0 N2 , Theoretica l N2 , exces s ai r O2 , exces s ai r Inert s (assum e N2 ) 36.1 1 33.4 6 29.0 0 29.0 0 29.1 0 29.0 0 4.23 3

.68 8 .22 0 .22 0 1.15 8 .22 0 -2.88 7 .760 4 .572 3 .572 3 -.60 6 .572 3 7.46 4 -3.59 3 -2.87 1 -2.87 1 1.31 1 -2.87 1 13.7 7

10.8 4 8.2 4 8.2 4 8.6 5 8.2 4

a CR C Handboo k o f Applie d Engineerin g Science . 1970 . Clevelan d Rubbe r CO. , Press . b Felde r an d Rousseau . Elementar yPrinciple s o f Chemica l Processes . Secon d Edition . 1986 . Joh nWile yan d Sons . c Calculate d usin g th e equatio na + b*10" 2 T + c*10 _5 T 2 + d*10" 9 T 3 (wher e T i s i n Celsius ) t o calculat e hea t capacit yvalue s i n (J/gmo l °C) . Th e resultin g value s wer e multiplie d bya facto r o f .23884 6 t o conver t t o (Btu/lbmol e °F) .

sampcalchtm04(Is ) A . 1- 7P.2 6

Mole s o f Eac hPollutan t i nProduc t (M )

Fro mStep s (1 ) an d (2 )

c o 2 = o c + 0.2 1 H2 O = 2 o

c + . 2 o

c + .01 2 + .00 3 + . 3
N 2 , Theoretica l = 7.5 2 a + .10 2 °2 , exces s = 3
N 2 , exces s = 11. 3 o f strea mE 2 Us e 10 0 lb-mol e dr ybasi s o f strea mE 2 fo r estimatin g mole s o f inert s i n product s Inert s = 100-a- . 021-7.5 2 oc- . 102-3-11 . 3

Afte r substitutin g value s fo r AT , Hen- , MWCH 4 / an d M , th e followin g equatio n need s t o b e solved .

o c (1 6 lb/lbmole ) (23,87 5 Btu/lb ) = (o e + .021 ) (13.7 7 Btu/lbmo l °F ) (200 0 - 77 ) + (2o c +.2oc + .01 2 + .00 3 + .3 ) (10.8 4 Btu/lbmol°F ) (200 0 - 77 ) + (7.5 2 o

c + .102 ) (8.2 4 Btu/lbmol e °F ) (200 0 - 77 ) + ( 3 l bmoles ) (8.6 5 Btu/lbmole s °F ) (200 0 - 77 ) + (11. 3 lbmoles ) (8.2 4 Btu/lbmoles°F ) (200 0 - 77 ) + (10 0 - o

c - .02 1 - 7.5 2 o

c - .10 2 - 3 - 11.3 ) (8.24 ) (200 0 - 77 )
Simplifyin g result s in : 382,00 0 a = ( a + .021 ) (26,480 ) + (2.2 a + .315 ) (20,845 )

+ (7.5 2 a + .102 ) (15,846 ) + 49,90 2 + 179,06 0 + (85.5 6 - 8.52a ) (15,846 ) 325,50 7 a = 1,593,48 4 Solvin g fo r a lead s to : a = 4.9 0

sampcalchtn>04(ls ) A.1 - 8P.2 7

(4 ) Determinin g th e compositio no f strea mE 2 Th e strea m

exitin g scrubbe r (E2 ) ha s th e followin g compositio n o n a 10 0 l bmol e dr ybasis : HC l = 9. 3 xIO" 5 l bmole s Cl 2 = 7. 5 xIO" 5 l bmole s CO2 , Haloge n= .02 1 l bmole s CO2 , Fue l = a = 4. 9 l bmole s N 2 , Theoretical , Haloge n = - 1 0 2 l bmole s N2 , Theoretical , Fue l = 7.5 2 a = 36.8 5 l bmole s O2 , Exces s Ai r = 3 l bmole s N2 , Exces s Ai r = 11. 3 l bmole s Tota l = 56.1 9 However , strea m

E 2 mus t hav e 10 0 lb-mole s o na dr ybasis . Therefore , 100-56.1 9 o r 43.8 1 lb-mole s o f som e iner t (assum e N 2 ) mus t b e i n strea m E 2 (5 ) Determinin g th e concentratio n o f th e VO C molecul e i nstrea mW Assumin g th e quantit yo f inert s doe s no t chang e acros s th e scrubbe r an d incinerator , th e wast e strea mmus t hav e th e followin g composition : Haiogenate d mode l molecul e = 0.007 2 l bmole s (Ste p (1) )

Inert s (N2 ) = 43.8 1 l bmole s (Ste p (4) )

Concentratio no f y(ppmv ) = y(lb-moles ) sumo f components(lb-moles ) x( 1 x10 '

Concentratio n of

VOC = 007 2 43.8 1 + .007 2 x

( 1 x 1 0 ) = 16 4 ppmvd

» 16 0 ppmvd

s amp c alchtm

O4(Is ) A . 1- 9P.2 8

A. 2 CALCULATIONO F METHO D 26 ADETECTIONLIMI TAPPENDI XA. 2 CALCULATIO NO F METHO D 26 ADETECTIO NLIMI T Metho d 26 A Analytica l Detectio n Limit : 0. 1 /xg/m l Th e samplin g detectio nlimi t wil l b e calculate d fro mth e analytica l detectio n limi t an d th e formula s presente d i nth e calculationa l procedure s sectio no f th e Tes t Method . Th e concentratio no f th e haiogenate d molecul e bein g sample d i s calculate d fro mth e equation : (1 ) c = km/V mst d where : c = concentratio no f haiogenate d molecule , mg/dsc m k = 10~ 3 mg//x

g m= /x g HC l i nsampl e (se e ste p 2 ) V ms t d = mete r bo xsamplin g volum e a t standar d

conditions , dsc m (2 ) m= 1.02 8 SV s where : m= /x

g HC l i n th e sampl e S = concentratio no f sample , /x g Cl~/m l (us e th e analytica l detectio n limit , 0. 1 /xg/ml ) V s = volum e o f filtere d an d dilute d sample , m l (assum e 100 0 ml ) m= 1.02 8 x0. 1 x100 0 = 102. 8 /xg . ( 3 ) v m,st d i s calculate d usin g th e followin g equation : V m ,st d = (t ) (Q ) where : t = samplin g time.minute s

Q = mete r bo xsamplin g rate , liters/minut e Assum e th e mete r bo xi s a t standar d condition s ( 1 atm , 68 ° F) , an d th e stac k exi t ga s i s bein g sample d fo r 6 0 minute s a t 2 1 liters/min .

monparhtm04(ls ) A . 2 — 1P.3 0

m 3 Vm,st d = (60 ) (21 ) —-—

_=1.2 6 dscm 100 0 1

Th e concentratio n i s the n

c = (10~ 3 ) (102-8 ) = 008 2 /dscm

1.2 6 * '

I nthi s cas e th e concentratio n i s als o th e sampling detectio n limit . Avalu e o f 5 time s th e detectio n limi t is : 5 xDetectio n limi t = (0.082 ) (5 ) = .41 0 ___. 5 mg/dscm

monparhtm O 4(ls ) A. 2 —2