p. 1



# RCRA Box 1883 Prepped by Ollie Stewart



### Document

Number: 

# 106) 1 ll-B-26 8 Docket Number: 

# A-90-1 9

Printed 12/3/200810:42:17AM Sheet 106 of 171P. 2

MEMORANDU

M
DATE : TO : FROM : SUBJECT : 

## A-90-1 9 ll-B-26 8

Februar y 10 , 199 2 \ cpp^^^S^- Lesli e B . Evans an

dDebbi e Stackhouse , EP A (MD-13 ) Ro y V . Oommen , Radia

n Limit s an

d Monitorin

g Parameter s fo

r Combustion/Scrubbin g System

s Use dto Contro l Halogenate

d Proces s Vent Stream s
SUMMAR Y Th e propose

d hazardou s organi c NESHA P wil l require combustio

ncontro l o

f som e proces s ven

t streams . Wher e halogenate

d stream

s are combusted , scrubber s woul db e require

d t o reduc e emission s of halogen s an dhydroge

nhalides . Thi s memorandu

m present s technica l suppor t fo r th e emissio

nlimit s an

d monitorin

g parameter s fo

r combustion/scrubbin g system

s use d t o contro l halogenate

d proces s ven

t streams . Dat a fo r establishin

g th e limit s wer e gathere dfro m a surve

y of facilitie s producin g ethylen e dichloride compounds . Tw o provision s are bein g considere

d b y th e U.S . Environmenta l Protectio nAgenc y (EPA ) fo

r inclusio

ni nth e propose d standar

d fo r proces s vent emissions : (1 ) a scrubber woul d b e require

d after a

nincinerator , boiler , o r proces s heater i f th e tota l concentratio nof halogenate

dpollutant s enterin g th e combustio

ndevic e i s greater tha n10 0 part s per millio nvolum e dr y (ppmvd) , an

d (2 ) th

e scrubber woul db

e require

d t o hav

e a tota l halogencontro l efficienc y of 9 9 percent . A

noutle t concentratio

nlimi t of 0. 5 milligram s per dr

y standar

d cubi c meter (mg/dscm ) ma

y b e provide

da s a nalternativ

e t o th e percent reductio

nfo r stream

s wher e 9 9 percent contro l woul dresul t i n outle t level s belo

w th e detectio

nlimi t an

dtherefor e b

e unmeasurable . Thi s memorandu m provide s technica l informatio n supportin

g thes e provisions .

Bonp»rht_o0 4 (It )P. 3

Th e propose

d EP A Tes t Metho

d26 A i s recommende

d t o measur e th e concentration s exitin g th e scrubber an

dt o confir

m th e contro l efficienc

y of th e scrubber durin

g th e require

dinitia l performanc e test . To ensur e th

e scrubber continue s t o mee t th e standard s after th e performanc e test , th e p H of th e effluent scrubber solutio n fro m th e las t scrubber stage an d th e liquid-to-ga s rati o (L/G ) woul d b e monitored . Further elaboratio

ni s presente

d i nth e followin

g sections : Introductio

n(1.0) , Dat a Collectio n(2.0) , Scrubber Parameter s fo r Surveye

d Facilitie s (3.0) , Potentia l Provision s fo r th e Standar d (4.0) , Measurement Technique s (5.0) , Scrubber Monitorin g Parameter s (6.0) , an d Reference s (7.0) . 1. 0 INTRODUCTIO

N As par t o f th

e Hazardou s Organi c NESHA P (HON ) development , th e EP A ha s identifie

d combustio

na s a viabl e metho dfo r controllin

g emission s of organi c pollutants . However , th e combustio

no f halogenate

dorgani c compound s (i.e. , organi c compound s containin g chlorine , fluorine , etc. ) ma y resul t i

nth e formatio

nan d emissio

no f specie s suc

ha s hydroge

nchlorid

e (HCl) , hydrogenfluorid e (HF) , an

d chlorin

e (Cl 2 ) whichare als o o nth e lis t of 19 0 hazardou s ai r pollutant s under Titl e II I of th e Clea nAi r Ac t Amendments . T o ensur e tha t combustio nof halogenated pollutant s wil l no t adversely impac t th

e environment , a secondar

y contro l devic e ( a scrubber ) i s neede dt o reduc e emission s generate

d b y th e primar

y contro l devic e (incinerator , boiler , o

r proces s heater) . 2. 0 DAT

A COLLECTIO

N A surve y o f chemica l facilitie s producin g halogenate

d compound s wa s conducte dt o identify

th e mos t commo

ntype s of secondar

y contro l device s currentl y i nuse , an

dth e resultin

g aci d ga s emission s fro m them . Inorder t o make th e surve y manageable , th

e scop e wa s limite

d t o chemica l facilitie s producin

g ethylen

e dichloride (EDC) . Ethylen e dichloride wa s

monparhtmO*(Is ) 2P. 4

chose nbecaus e i t i s produce d i nlarg e quantities , an

dfacilitie s producin

g ED C woul d b

e expecte

dt o hav

e larg e aci dga s release s and/or secondar

y pollutio

ncontro l device s i nplace . A

tota l of fiv e companie s (BFGoodrich , Borden , Dow , Occidental , an d PPG ) i

n eight location s wer e surveyed. 1 " 1 3 Fou r o f th e eight plant site s produc e vinyl chloride , an d on e produce s polyviny l chloride , a s wel l a s EDC . Tabl e 1 present s th e ED C productio

ncapacitie s of th

e eigh t facilities , thei r primar y an dsecondar

y ai r pollutio

ncontro l devices , an

d th e halogenate

d pollutant s emitte dfro m thei r primar y contro l device . Seve no f th e eigh t facilitie s reporte d therma l incineratio na s th e primar

y contro l device . Th e exceptio

ni s Do w Chemical' s Freepor t plant , whichreporte d tha t proces s vent 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 db y thi s facility . Chlorin

e ga s an

d HC l are th

e mos t commo

nhalogenate

d pollutant s emitte

d fro m th e incinerator s at th e seve nfacilities . Althoug honly on e o f th e eight facilitie s reporte dusin g flare s a s th

e primar

y contro l device , bothth e Texa s Ai r Contro l Boar d (TACB) 1 ** 1 6 an

d th e Louisian

a Ai r Contro l Boar

d(LACB) 1 7 indicate

d tha t flare s are not prohibite dfro m bein g use d t o contro l halogenate

d ga s stream

s inthei r States . However , th e TACB an d LACB als o indicate dtha t flare s are no t normall y used , an d ar e usuall y

discourage

dfro m bein g use d fo r thi s purpose . Neithe r th

e TACB o

r LACB impos e concentratio nlimit s o

n halogenate

d compound s enterin g flares , s o flare applicabilit y i s determine

d o na case-by-cas e basi s usin g dispersio

nmodeling . 3. 0 SCRUBBE

RPARAMETER S FO

RSURVEYE

D FACILITIE S The seve

nfacilitie s reportin g incineratio

na s th e primar

y contro l devic e als o reporte dwe t scrubber s a s th e secondar

y contro l device . Tabl e 1 present s som e o f th e characteristic s of th e scrubbers . Al l o f th e scrubber s us e packe d columns ; sixus e causti c a s th

e scrubbin

g solvent an

don e use s water .

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

PLAN T COD E COMPAN Y LOCATIO N ED C PRODUCTIO N CAPACIT Y (M M Kg/yr ) PRIMAR Y

CONTRO L DEVIC E COMPOUND S EXITIN G PRIMAR Y DEVIC E SECONDAR Y

CONTRO L DEVIC E COLUM N

TYP E SCRUBBIN G

OPERATIO NSOLVEN T

A 2 ' 3 BFGOODRIC H L A PORT E B 3 ' 4 BORDE N

GEISMA R

DO W

D 3. 5 QO H

,3. 5

G H DO W
OCCIDENTA L OCCIDENTA L PP G FREEPOR T

OYSTE RCREE K

PLAQUEMIN E T X

LA

T X

T X

LA 72 0

33 9

72 7 INCINERATO R

INCINERATO R

FLAR E C1- , HC l

C1- , HC l Trac e Amount s o f Othe r Halogen s Trac e Amount s o f Halogenate d SCRUBBE R SCRUBBE R

NON E PACKE D

PACKE D

N D RECYCL

E CAUSTI C RECYCL E WATE

R

N D N D

CORPU S CHRIST I T X CONVEN T L A LAK E CHARLE S L A 50 0

77 3
36 4 36 4 122 7 INCINERATO R

INCINERATO R
INCINERATO R INCINERATO R INCINERATO R Compound s

Cl 2 , HC l Trac e Amount s o f Othe r Halogen s ci 2 , ci 2 , ci 2 , ci 2 , HC l
HC l HC l HC l SCRUBBE R

SCRUBBE R
SCRUBBE R SCRUBBE R SCRUBBE R PACKE D

PACKE D
PACKE D PACKE D PACKE D RECYCL E

ONC E THROUG H RECYCL E RECYCL E RECYCL E CAUSTI C

CAUSTI C
CAUSTI C CAUSTI C CAUSTI C

N D n o dat a 1 Reference s 1-1 3 * 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. 6

Tabl e 2 present s th e reporte

d informatio

no nth e performanc e of eac hscrubber , including : acid ga s (HCl an d Cl 2 ) outle t concentrations , tes t method s use dfo r determinin

g aci dga s concentrations , HC l desig nremova l efficiency , p H of scrubbin

g liquid , exitin

g temperature of th e effluent gas , an

dth e maximu

m flo w rat e o f effluent gas . Fo r th e surveye

dfacilities , Tabl e 2 indicate s only

tw o pollutants , HC l an dCI2 , wer e reporte dexitin

g th e scrubber . Figur e 1 present s th e HC l an

d CI 2 concentration s i nth e effluent ga s fro

m th e scrubbers , b

y facility . Hydroge n chlorid e emission s range

dfro m 0.9 3 ppmv

d t o 7 2 ppmvd , witha n average value o f 3 3 ppmvd . Chlorin e emissio

nlevel s range

d fro m 0.7 5 ppmv

d t o 2 6 ppmvd , witha naverage valu

e o f 1 1 ppmvd . Al l emission s dat a ar e correcte dt o 3 percent oxyge nbasi s t o correlat e withth

e propose

dHO N standards . A s Tabl e 2 indicates , 8 o f th e 1 0 scrubber s hav

e HC l desig

n 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 desig nremova l efficiencie s of 9 8 an d9 7 percent , respectively . Al l bu t on e we t scrubber use s causti c a s th e solvent , withpH' s rangin g fro m 7. 5 t o 10.5 . Th

e exceptio

ni s Facilit

y B (Borden) , whichuse s water a s th e scrubbin

g liquid . Al l but on e of th e outle t ga s temperature s wer e betwee n10 0 an

d 18 8 degree s Fahrenheit . Th e exceptio

ni s Facilit

y G(Occidental) , whichreporte da valu

e of 38 9 degree s Fahrenheit . However , thi s value i s suspect , a s i t i s abov e th e boilin

g point o f water . Effluent ga s flo w rate s range fro m 1,97 7 dscf

m t o 33,70 3 dscfm . 4. 0 POTENTIA

L PROVISION S FO

RTH E STANDAR

D Tw o provision s fo

r combustor/scrubber system s are bein

g considere

d b y th e EP A fo r inclusio

ni nth e HO N standard : (1 ) scrubbin

g i s require

d i f th e inle t concentratio nt o th e incinerator , boiler , or proces s heate r i s greate r tha n10 0 ppmv

d of halogenated organi c compounds , an d(2 ) scrubber s mus t hav e a tota l halogenan

d hydrogenhalide contro l efficienc y o f 9 9 percen t o

na mola r basis .
monparhtml H (-» ) 5Tabl e 2 . Scrubbe r Characteristic s o f th e Surveye d Facilitie s

OD E

A B C D

E F

G H COMPAN Y
BFGOODRIC H BORDE N DO W DO W

DO W OCCIDENTA L

OCCIDENTA L PP G SCRUBBE R

NUMBE R

A- 1 B- 1 C- 1 D- l D- 2 D- 3 E- 1 F- l F- 2 G- 1 H- l H- 2 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 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 RUBBE R DAT 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 Ci 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

* = Typica l flo

w ND = N o Dat a8 0 

# Figur e 1
. HC I an d CI 2 Emission s Outle t Fro m Scrubbe r

7 0 - D l l
D O K 1 0 

### 0
T J > 

### E a u 6 0

5 0

4 0 D a

c o o i . *-. c • » o C o o 3 0

2 0 D

1 0 

### a 

# + A - 1 B - 1 

### C- 1 

### I D-2 

### I EM I D - 1 D- 3

SCRUBBER S D



# ~A'A F- 1 C I

I I t I I I H L) HC l fcmission s + Cl 2 Emissium

.P. 9

N o informatio n wa s availabl e fro mM C 1 2 incinerator/scrubbe r installation s o n th e amoun t o f halogenate 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 n th e incinerato r outlet . Th e incinerato r inle t halogenate d organi c compoun d level s wer e therefor e calculate d base d o n th e combustio n o f a mode l halogenate d organi c molecul e an d th e reporte d scrubbe r outle t concentration s presente d i n Tabl e 2 . Th e mode l halogenate d compoun d wa s develope d b

yth e EP

Ai n a previou s study. 1 Th e concentratio n o 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 efficienc yo f 9 9 percen t fo r HC l an

d 9 5 percen t fo r CI 2 (se e Appendi x A. l fo r sampl e calculations) . Tabl e 3 present s th e calculate d inle t halogenate 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 n levels , an d abou t 16 0 ppmv

d fo r a scrubbe r reporting bot h HC 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 halogenate d organi c compound s entering a n incinerator , boiler , o r proces s heate r tha t woul d requir e subsequen t scrubbing . Thi s approac h wa s take n becaus 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 surve ydata , an d applicabilit yan

d performanc e o f scrubber s t o stream s wit h outle t haloge n level 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 halogenate d organi c concentration s abov e 10 0 ppmv d canno t b e introduce d t o a flare .

DonpaxhtmO*(Is )P.1 0

Tabl e 3 . Mode l Halogenate d Compoun d

Concentration s fo r Surveye d Facilitie s

COD E
A B C D

E F

G H COMPAN

Y
BFGOODRIC H BORDEN DO W DO W

DO W OCCIDENTAL

OCCIDENTAL PP G SCRUBBE R

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

INCINERATOR INLE T CONCENTRATION (ppmvd )
16 4 3,27 2 ND 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 nonl y a s chlorin e wa s no t provided .P.1 1

Eigh t o f th e te nfacilitie s i nth e databas e reporte d anHC l desig nremova l efficienc y o f a t leas t 9 9 percen t wit hsom e a s hig ha s 99. 9 percent . Th e remainin g tw o reporte d 9 7 an

d 9 8 percen t efficiencies . A surve y

o 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 nga s stream s i s achievable . Base d onthi s information , 9 9 percen t overal l contro l o f halogen s an d hydroge nhalide s fro m scrubber s woul d b e achievabl e an d coul d b e include d a s a provisio nt o th e propose d standard . Haloge nremova l may b e slightl y

lowe r tha nhydroge nhalides , bu t haloge nconcentration s a t scrubbe r inlet s an d outlet s ar e generall y expecte d t o b e lowe r tha nfo r hydroge nhalides . 5. 0 MEASUREMEN T TECHNIQUE S I norde r t o demonstrat e 9 9 percen t control , outle t concentration s fro m th e scrubbe r a s lo w a s 0. 8 ppmv

d may nee dt 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) . A memorandu

m fro m Terr y Harriso no f th e EPA , date d Augus t 9 , 1991, Z 1 indicate d tha t EPA Metho d 2 6 an

d propose d Metho d 26 A ar e applicabl e fo r measurement s a t thes e levels . Bot hmethod s ca nb e use d t o measur e th e followin g halogen s an

d hydroge nhalides : HCl , HF , hydroge nbromid e (HBr) , Cl 2 , and Br 2 . Metho d 2 6 i s use d fo r non-isokineti c sampling . Metho d 26 A

i 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 nhalide s exitin g th e scrubbe r wil l b e entraine d i nmoistur e droplets . Therefore , isokineti c samplin g usin g Metho d 26 A i s th e recommende d measuremen t method . However , Metho d 26 A tend s to sho

w a bia s fo r lowe r concentrations . Th e metho d i s currentl y unde r review

b y th e EPA

to resolv e thes e issues . Th e lowe r analytica l detectio nlimi t o f Metho d 26 A i s approximatel y

0.0 8 mg/dscm

(se e calculation s i nAttachmen t A.2) . A standar d facto r o f 5 time s th e detectio nlimi t result s i na n alternat e lowe r cutof f o f approximatel y 0. 5 mg/dscm . I f a facilit y

ca ndemonstrat e a noutle t concentratio nbelo w monp«rh_mO * (la ) 1 00. 5 mg/dsc m fo r eac hhaloge

no r hydroge

nhalid e specie s present , th e propose

d regulatio

ncoul dspecify

tha t th

e facilit

y woul d b

e considere

d t o b e i ncomplianc e an

d th e inle t concentratio nwoul d not hav e t o b e measure

d an d percent reductio

nwoul dnot nee

d t o b e calculated . Thi s alternat e concentratio nleve l i s neede

d becaus e facilitie s ca nno t reliabl y

measur e concentration s belo w 0. 5 mg/dscm . 6. 0 SCRUBBE

RMONITORIN

GPARAMETER S AN

D LIMIT S Th e appropriat e monitorin g parameter s t o ensur e scrubber complianc e wit hth

e standar

dare th

e p H o f th e effluen t fro

m th e las t scrubbe r stage , an d th e liquid-to-ga s (L/G ) ratio . The p H of th e effluent fro

m th e las t scrubber stage i s a n indicator o f it s acidit y (i.e. , amount o f aci d ga s dissolved) . I f th e p H i s lower tha

nnormal , th

e scrubber i s unlikel y t o b e removin g sufficient aci di nth e ga s t o operat e at th e specifie

d efficienc

y o r t o mee t th

e propose

dregulation . Th

e p H value necessar

y t o achiev

e performanc e requirement s ca nb e determine

d b y operatin

g at th e maximu

m haloge nmas s flo

w rat e durin

g th e initia l performanc e test . Durin g subsequent operation , th e average p

H shoul d b

e maintaine

dat a leve l no t les s tha n1 p H uni t belo

w th e value measure

ddurin g th e performanc e test . Th e average operatin

g p H value s woul db

e determine

ddurin g 3-hou r measuremen t periods . Thi s 3-hou r averagin

g perio di s consistent withth e averagin

g perio d use d fo r al l o f th

e other proces s vent , combustion , an

d recover

y devic e monitorin

g parameter s i

nth e propose d HO N regulation . Th

e p H ca nb e monitore

dusin g a monitorin

g devic e wit ha continuou s recorder , whichar e readily availabl e fro

m vendors . Monitorin

g th e p H alon e wil l no t adequatel y indicat e whethe r th e scrubbe r i s operatin g properl y

t o mee t th

e propose

d regulation . Fo

r example , a p

H change ma

y als o indicat e th

e ga s flo w rat e i s smalle r o

r larger tha

nat norma l operatin g conditions . The pH coul d b e withi nthe propose dlimits , but th

e aci d ga s contro l efficienc y o f th e scrubber coul db

e reduce

d i f th e liquid-to-ga s contac t withi nth e scrubber i s belo

w norma l levels . Therefore , th e L/ Grati o shoul dals o b e monitored . Decrease

d L/ Gvalue s indicat e a smaller liqui do r larger ga s flo

w
-»np»rhtmO*(l» ) 1 1P.1 3

rate , wit ha resultan t declin e i nperformance . A t maximu m operatin g load(i.e. , whe nGi s large) , th e L/ Grati o tend s towar da minimu

m value . Th e minimu m L/ Grati o necessar y t o achiev e th e performanc e requirement s shoul db e se t a s a limitin g parameter . Th e L/ Gvalu e woul db e determine ddurin g th e performanc e tes t whil e th e proces s uni t i s operatin g a t minimu m liqui dflow

andmaximu

m ga s flo

w rate s andachievin g 9 9 percen t removal . Th e scrubbe r woul dthe nb e require dt o monito r L/ Gan d repor t an

y 3-hou r perio dwhe nth e averag e L/ Gi s mor e tha n 5 percen t below

th e averag e valu e measure ddurin g th e performanc e test . Th e liqui dandga s flo w rate s ca nb e measure dusin g continuou s flo

w meter s whic har e availabl e fro m vendors . Th e flow meter s woul db e installe da t th e ga s andliqui dinlet s t o th e scrubber .

monp«xhtm04(_s ) 1 2P.1 4

7. 0 REFERENCE S 1 . Questionnair e respons e fro m Gustafson , David , Do w Chemical , Midland , MI , t o Oommen , R.V. , Radian . Ma y 22 , 1991 . Fa

xof respons e t o question s concernin g scrubber exi t concentrations . 2 . Questionnair e respons e fro m Gustafson , David , Do w Chemical , Midland , M I t o Oommen , R.V. , Radian . Ma y l , 1991 . Fa

xof questionnair e o

nparameter s of scrubber exi t gas . 3 . Questionnair e respons e fro m Gustafson , David , Do w Chemical , Midland , MI , t o Oommen , R.V. , Radian . Apri l 26 , 1991 . Fa xof respons e t o question s concernin g parameter s of th

e scrubber exi t gas . 4 . Questionnair e respons e fro m Arnold , Sherrie , Do w Chemical , Midland , M I t o Oommen , R.V. , Radian . March26 , 1991 . Fa xof questionnair e o

ncontro l technologie s use dt o trea t proces s vent streams . 5 . Questionnair e respons e fro m Emery , Elizabeth , Borde n Chemical s an

d Plastics , Geismar , LA , t o Oommen , R.V. , Radian . Ma

y 2 , 1991 . Fa

xof questionnair e o nparameter s of scrubbe r exi t gas . 6 . Questionnair e respons e fro m Emery , Elizabeth , Borde n Chemical s an

d Plastics , Geismer , LA , t o Oommen , R.V. , Radian . Apri l 1 , 1991 . Fa xof questionnair e o ncontro l technologie s use

d t o trea t proces s vent streams . 7 . Questionnair e respons e fro m Hinson , David , B

F Goodric

h Intermediates , L

a Porte , TX , t o Oommen , R.V. , Radian . Apri l 30 , 1991 . Fa

xo f incinerator an dstack data . 8 . Questionnair e respons e fro m Hinson , David , B

F Goodric

h Intermediates , L

a Porte , T

Xt o Oommen , R.V. , Radian . Apri l 2 , 1991 . Fa

xo f questionnair e o ncontro l technologie s use d t o trea t proces s vent streams . 9 . Telecon . Oommen , R.V. , Radia nwithLiggio , Esther , PPG , Environmenta l Engineer , Ma y 10 , 1991 . Teleco

nabout scrubber exi t ga s parameters . 10 . Questionnair e respons e fro m Liggio , Esther , PP GChemicals , Lake Charles , LA , t o Oommen , R.V. , Radian , Ma y 8 , 1991 . Fa

x o f questionnair e o

ncontro l technologie s use dt o trea t proces s vent emissions . 11 . Lette r fro

m Ewen , Kelly , Occidenta l Chemica l Corporation , Convent , LA , t o Oommen , R.V. , Radian . Apri l 24 , 1991 , Letter concernin

g parameter s o f scrubber exi t gas .

monparhtm

O * (Is ) 1 3P.1 5

12 . Telecon . Wilson , Jim , Occidenta l Chemica l Co. , Corpu s Christi , TX , withOommen , R.V. , Radian , Apri l 22 , 1991 , Teleco nof respons e t o question s about scrubber exi t ga s parameters . 13 . Questionnair e respons e fro m Takacs , Lazlo , Occidenta l Chemica l Center , Niagara Falls , NY , t o Oommen , R.V. , Radian . March26 , 1991 . Fa

xo f questionnair e o ncontro l technologie s use d t o trea t proces s vent streams . 14 . Telecon . Oommen , R.V. , Radian , withHome , Karen , Texa s Ai r Contro l Board . Ma

y 15 , 1991 . Teleco

no nflare use . 15 . Telecon . Oommen , R.V. , Radian , withOlsen , Karen , Texa s Ai r Contro l Board . Apri l 25 , 1991 . Teleco no nflare use . 16 . Telecon . Disorbo , S. , Radian , withSaitas , J. , Texa s Ai r Contro l Board . Apri l 26 , 1991 . Teleco no nflare use . 17 . Telecon . Oommen , R.V. , Radian , withDavis , B. , Louisian a Ai r Contro l Board . Ma y 17 , 1991 . Teleco

no nflare use . 18 . Organi c Chemica l Manufacturin g Volum e 4 : Combustio

nContro l Devices , EPA-450/3-80-026 . Offic e o f Ai r Quality Plannin

g an d Standards , U.S . Environmenta l Protectio nAgency . 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 m Harrison , Terry , EMB/EP A t o Oommen , R.V. . Radian . Augus t 9 , 1991 , Fa xo f applicabl e tes t method s fo r measurin

g halogen s fro

m scrubbers .

m«np»rhtm0 * (Is ) 1 4P.1 6

APPENDI XA
A. l SAMPLE CALCULATIO N FO RMODEL HALOGENATE

D COMPOUN

D CONCENTRATIONS A

T THE INCINERATO

RINLET A. 2 CALCULATIO

N O F METHO D 26 A DETECTIO

N LIMI T

monptrhtaOM-s )P.1 7

A. l SAMPL E CALCULATIONP.1 8

A. l SAMPLE CALCULATIO N O F THE MODEL HALOGENATE D COMPOUN

D CONCENTRATIO

N A T THE INCINERATO

RINLET
PURPOSE : Th

e objectiv

e of thi s sectio

ni s t o present exampl e calculation s fo

r estimatin

g th e halogenate

dorgani c compoun d concentratio

nenterin

g a nincinerator tha t correlate s t o specifi c scrubber outle t HC l an dCI 2 concentrations . FLO W DIAGRAM : Th

e basi c block flo

w diagra m o f th e pollutio

n contro l syste

m i s represente

das :

Wast e Strea

m (W ) Incinerator Effluent Strea m 1 (Ei ) Scrubber Effluent Strea m 2 (E 2 ) >

Th e scrubber i s assume dt o b e 9 9 percent efficient fo r HC l control , an

d 9 5 percent efficient fo r CI 2 contro l base d o nth e informatio

ncollecte

d an dga s absorber vendor surveys . PROCEDURE : Sinc e th

e onl y informatio

nknow ni s th e HC l an

dCI 2 scrubber outle t concentrations , th e followin

g procedure s wil l b e used . 1 . Fro

m pollutan t concentration s i nE 2 an dremova l efficiencies , pollutant concentration s i nE ^ wil l b

e calculated . 2 . Fro

m pollutant concentration s i nE i an dstoichiometri c balances , th

e halogenate

d organi c compoun

d concentratio

no f W wil l b e calculated , takin g int o account dilutio

nai r requirements .

sampctlchtmO * (Is ) A . 1- 1P.1 9

A.1. 1 CALCULATIO NO F MODE L HALOGENATE D ORGANI C COMPOUN D
Apreviou s EP Aprojec t establishe d a mode l halogenate d VO C molecul e wit h th e followin g composition: " byweigh t percen t 34.3 % Carbo n 4.7 % Hydroge n 60.6 % Chlorin e
T o conver t t o moles , assum e 10 0 l b basis :

Carbon : 34. 3 l b • } *TM°\*- 2.8 6 l b mol e 12.0 1 l b
Hydrogen : 4. 7 l b l b mol e 1.00 8 l b - 4.6 6 l b mole s

Chlorine : 60. 6 l b l b mol e 35. 5 l b - 1.7 1 l b mole s

c 2.8 6 H 4.6 6 cl 1.7 1

"Organi c Chemica l Manufacturin g Volume 4 : Combustio n Contro l Devices , EPA-450/3-80-026 . Offic e o f Ai r Qualit y Plannin g and Standards , U.S . Environmenta l Protectio nAgency . s«_pc«lehtm0*(ls ) A . 1- 2A.1. 2 CALCULATION O F HALOGENATE D ORGANI C COMPOUND CONCENTRATION I N WAST E STREA

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

m scrubbe r =3 % oxyge ni nEffluen t (dr y basis ) strea

m 2 (E2 )
A nexampl e calculatio nwil l b e presente d usin g scrubbe r outle t dat a fro

m th 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 nvalue s ar e converte d t o mol e % value s usin g 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 ) ( .751 = 7. 5 xIO" 5 10 © Par t 1 : Calculatio no f Effluen t Strea m 1 (E^ l
Th e dry

compositio no 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 dry basis . I f strea

m E 2 contain s 3 % O 2 the ni t woul d hav e 3 lb-mole s o f O 2 (10 0 lb-mole s x.03 ) i nit . Th e strea m enterin g th e scrubbe r i s calculate d fro

m th e followin g balance .

smpca.ehtaOt(-s ) A . 1 — 3P.2 1

Assuming 9 9 % efficienc yfo r HCl : *E 2
HCl , E l . _efficienc y

10 0 HC l 1 - E 2 _

, 9. 3 x 1 0 9 9 .0 1 009 3 l b mole s 10 0

Wher e X E 2 i s th e concentratio n o f a halogenate d specie s i n strea m E 2 an d X^i s th e concentratio n o f th e halogenate d specie s i n Ej_. ' Assumin g 9 5 % efficienc yfo r CI2 :

Cl . Cl 2 E2 .

1 - 9 5 10 0 7. 5 x 1 0

.0 5 - 5 001 5 l b mole s

E x + z HC l « - .009 3 l b mole s CI 2 ~ .001 5 l b mole s Inert s = wl b mole s — > CO 2 = = x l b mole s N 2 = yl b mole s Q. 2 = 3 l b mole s wate r = z lb-mole s Scrubbe r 99 % HC l 95 % Cl 2 E 2 + Z

HC l = 9. 3 x 10~ 5 l b mole s Cl 2 = 7. 5 x IO - 5 l b mole s

— > Inert s = wl b mole s CO 2 a x l b mole s N 2 = yl b mole s 0 2 • 3 l b mole s wate r = z l b mole s Assum e CO2

- N2 , an

d O 2 d o no t chang e acros s th e scrubber .

sampcalchtaO*<Is ) A . 1- 4P.2 2

Exampl e Case : (Continued )
Par t 2 : Calculatio no f halogenate d organi c compound concentratio ni nwast e strea m (W . Th e followin g diagra m present s th e flo w stream s enterin g an d exitin g th e incinerator :

Fue l (CH4 ) Theoretica l ai r
W

c 2.8 6 H 4 . 6 6 C1J..7 ! + Inert s (Assum

e N2 ) i i

Incinerato r E

x+ Z

Dilutio nAi r HC l = .009 3 l bmole s CI 2 = .001 5 l bmole s Inert s = w

l bmole s CO 2 a xl bmole s N 2 = y l bmole s 0 ; = - 3 l bmole s Wate r = z l bmole s
Th e concentratio no f th e halogenate d molecul e enterin g th e incinerato r i nstrea m W wil l b e calculate d fro m th e stoichiometr y o f th e combustio no f th e halogenate d molecul e an d fuel , an

dth e subsequen t enthalpy balance . (1 ) Stoichiometr y o f Halogenate d Organi c Compound 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 ni ntheoretica l air , dilutio nair , and moistur e i ntheoretica l ai r an d dilutio nai r nee d t o b e calculated . 1 . Theoretica l O 2 neede d = [(mole s H2O ) (Oxygenatom s i nH2O ) + (Mole s CO2 ) (Oxyge natom s i nCO2)]/Oxyge natom 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 no f O 2 i nAi r
= [0.02 7 mole s O2/.2I ] = .12 9 l bmole s ai r 3 . Nitroge ni ntheoretica l ai r
= (Theoretica l air ) (fractiono 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 0 2 /.21 ] = 14. 3 l bmole s
sampcslchtmO*(Is ) A . 1- 5P.2 3

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 bdry air. " Moistur e = .12 9 l bmole s ai r * (29. 1 l bair/l bmol e air) *

.01 3 l bwater/l bdry ai r * (lbmol e water/1 8 lbs )

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

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

.01 3 l bwater/l bdry ai r * (lbmol e water/1 8 lbs )

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

o CH 4 + 2 a 0 2 — > a C0 2 + 2 a H 2 0 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 ni ntheoretica 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 y air . Moistur e = 9.5 2 a l bmole s ai r * (29. 1 l bair/l bmol e air) *

.01 3 l bwater/l bdry ai r * (lbmol e water/1 8 lbs )

= . 2 a l bmole s wate r (3 ) Enthalpy

Balanc e A nenthalpy

balanc e i s require d t o estimat e th e valu e o f a • Assume hea t releas e fro m th e combustio no f th e mode l compound i s insignificant . • Incinerato r operatin g temperatur e = 2,000° F (based onHO N incinerato r parameters ) Referenc e temperatur e = 77° F Hea t o f combustio no f CH 4 = Hea t gai nb y th e product s o f combustio n
"Felder , R.M . an

d Rousseau , R.W . Elementar y Principle s o f Chemica l Processes . Second Edition . 1986 . JohnWile y an dSons . sampealehtmOtda ) A . 1 — 6P.2 4

a H CH4 = (MCpAT) C 0 2 + (MCpAT) H o + ( MC p AT >N 2 theoretica l

+ (MC p 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 no f methan e = 23,87 5 Btu/lb a
M W CH 4 = 1 6 lb/l bmol e M = mole s o f eac hcompound 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 y o f th e product s o f combustio nliste d Hea t Capacit y

o f Compounds b Pollutan t Hea t Capacit y Coefficient s C p abe d (Btu/l bmole°F) c
C0 2 36.1 1 4.23 3 -2.88 7 7.46 4 H ? 0 33.4 6 .68 8 .760 4 -3.59 3 N 2 ' , Theoretica l 29.0 0 .22 0 .572 3 -2.87 1 N;> , exces s ai r 29.0 0 .22 0 .572 3 -2.87 1 0;> , exces s ai r 29.1 0 1.15 8 -.60 6 1.31 1 Inert s (assum

e N 2 ) 29.0 0 .22 0 .572 3 -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. Cleveland Rubbe r CO. , Press . D Felde r an

d Rousseau . Elementar y Principle s o f Chemica l Processes . Second Edition . 1986 . Joh nWile y and 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 nCelsius ) t o calculat e hea t capacit y value s i n (J/gmo l °C) . Th e resultin g value s wer e multiplie d b y a facto r o f .23884 6 t o conver t t o (Btu/lbmol e °F) .

_i__->c»_chtm0*(-« ) A . 1- 7P.2 5

Mole s of Eac

hPollutant i

nProduc t (M ) Fro m Step s (1 ) an

d (2 )

co 2 = <x + 0.2 1 H 2 0 = 2 « + . 2 « + .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 m E 2 Us e 10 0 lb-mol e dr

y basi s of strea

m E 2 fo r estimatin

g mole s of inert s inproduct s Inert s = 100-a-.021-7.5 2 «-.102-3-11. 3

Afte r substitutin

g value s fo

r AT , HCH 4 » MWCH4 » an d M , th e followin

g equatio

nneed s t o b

e solved .

o : (1 6 lb/lbmole ) (23,87 5 Btu/lb ) = (o c + .021 ) (13.7 7 Btu/lbmo l °F ) (200 0 - 77 ) + (2o e + .2 « + .01 2 + .00 3 + .3 ) (10.8 4 Btu/lbmol°F ) (200 0 - 77 ) + (7.5 2 « + .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 - « - .02 1 - 7.5 2 a - ,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

sampcalchtmOtds ) A . 1 — 8(4 ) Determinin g th e compositio no f strea m E 2
Th e strea

m exitin g scrubbe r (E2 ) ha s th e followin g compositio non a 10 0 l bmol e dry basis :
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 N 2 , Theoretical , Fue l = 7.5 2 a = 36.8 5 l bmole s 0 2 , Exces s Ai r = 3 l bmole s N 2 , 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 ona dry basis . 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 nstrea

m E 2 (5 ) Determinin g th e concentratio no f th e VO C molecul e i nstrea m W Assumin g th e quantit y o f inert s doe s no t chang e acros s th e scrubbe r and incinerator , th e wast e strea m mus t hav e th e followin g composition : Halogenate d mode l molecul e = 0.007 2 l bmole s (Step (1) )

Inert s (N2 ) 43.8 1 l bmole s (Step (4) )

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

Concentratio

nof VOC .007 2

43.8 1 + .007 2 x ( 1 x 10 6 ) » 16 4 ppmvd » 16 0 ppmvd

s___pc»_ehta.O*(l» ) A . 1- 9P.2 7

A. 2 CALCULATION

O F METHO D 26 A

DETECTION

LIMI TP.2 8

APPENDI XA. 2 CALCULATION

O F METHO D 26 A

DETECTION

LIMI T Metho d 2 6A Analytica l Detectio nLimit : 0. 1 nq/ml Th e samplin g detectio nlimi t wil l b e calculate d fro m th e analytica l detectio nlimi 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 halogenate d molecul e bein g sample di s calculate d fro

m th e equation : (1 ) c = km/Vms t d where : c = concentratio no f halogenate d molecule , mg/dscm k - 10" 3 mq/nq
m = /x g HC l i nsampl e (se e ste p 2 )

v m,st d ~ mete r boxsamplin g volume a t standar d

conditions , dscm (2 ) m = 1.02 8 SV s where : m

= nq HC l i nth e sampl e S = concentratio no f sample , /* g Cl~/m l (us e th e analytica l detectio nlimit , 0. 1 /xg/ml ) V s = volume 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 fiq.
(3 ) v m st d i s calculate d usin g th e followin g equation : Vm,st d - (t ) (Q ) where : t = samplin g time.minute s

Q = mete r bo xsamplin g rate , liters/minut e Assume th e mete r bo xi s a t standar d condition s ( 1 atm , 68 ° F) , and 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(_s ) A . 2 — 1P.2 9

3 Vm,std = (60 ) (21 ) —-— r =1.2 6 dscm 100 0 1

The concentratio

ni s the

n

c = (10~ 3 ) (102-8 )
_ . Q Q8 2 mg/dscm 1.2 6

Inthi s cas e th

e concentratio

ni s als o th

e samplin

g detectio

n limit . A

value o f 5 time s th e detectio

nlimi t is : 5 xDetectio

nlimi t = (0.082 ) (5 ) = .41 0 - . 5 mg/dsc m

nonpaxhtm04(ls ) A . 2— 2P.3 0



### ADDENDU M AP.3 1

HALOGENATE D STREAM DEFINITIO N

Th e conversio n o

f ppmv do f halogenate dmolecul e t o ppmv do f haloge n atom s i s base do n th e mode l molecul e a s follows : Mode l molecul e = C2.8 6 H4.6 6 CI17 1
Ther e ar e 1.7 1 mole s of

C l atom s pe r

mol e o f mode l molecule
. A t

atmospheri c conditions , volume fractio n (ppmvd ) i s equivalen t t o amol e fractio n (mole s halogen/mol e ven t

stream)
. Th e lowes t

calculate dvalu e fo

r CI2 an dHC l i s 16

4 ppmvd
. Th e lowes t

calculate dvalu e fo

r HC l only i s 13 2 ppmv d(se e Tabl e 3)
.
13 2 ppmvd

x A = 225. 7 ppmvd Cl atoms. mole model
16 4 ppmvd x 1J 1 mole °= 280. 4 ppmvd Cl atoms, mole model