P. 1



# OAR Box 

# 1870 Prepped by Ollie Stewart



# Document

Number: 

# 15 ) ll-A-2 0 Docket Number: 

# A-90-1 9

Printed 11/28/20087:05:04 AM Sheet 15of 67P. 2

',>• 

# SER & m\- _i

. .tr . **-?- » 4 i

Unite d State s Offic e o f Ai r Quality Environmenta l Protectio n Plannin g an d Standard s Agency Researc h Triangl e "--' Ai r 

## n 

# A-90-1 9 

# Benzen e n. A 

# -2 o Organi c Chemiuc . Manufacturin g Ethylbenzene/Styren e EM B Repor

t 79-OCM-1 5 Apri l 198 1



# Emissio n Tes t Repor t E l Pas o Product s Compan y Odessa , Texa s 

# l!)

0 0 IMJ 

# 1 W E SE P I • ( 199 2 EP A AI R DOCKE T



# I I I IP. 3



## 2. 0 SUMMAR

YAN D DISCUSSION

RESULT S
Th e samplin g andanalysi s dat a a t El Pas o Product s wer e obtaine d fro m two separat e proces s locations . Th e firs t wee k wa s spen t samplin g andanalyzin g th e fue l an dth e outle t gase s fro m th e stea

m superheater . Th e second wee k wa s spen t collectin g dat a fro m th e fue l ga s inle t an d th e exhaus t gase s o f th e ho t oi l heater . Th e ho t oi l heate r an d th e stea m superheate r ar e diagramme d i nFigur e 2-1 . Point s on e an d tw o wer e sample dsimultaneousl y andpoint s three , fou r an d fiv e wer e sample d simultaneousl y

i norde r t o determin e th e benzen e destructio nefficienc y o f th e combustio nprocesses . Figur e 2- 1 show s th e samplin g designation s nex t t o th e samplin g poin t number . Sample s wer e analyze d for :

a ) C0 2 

## , 0 2 

## , N 2 

## , H 2 

## , CH 4 

## b y GC/TCD . b ) Benzene , toluene , xylene , ethylbenzene , styren e b y GC/FID . c ) Lo w molecula r weigh t hydrocarbon s a s C_-C 6 

## specie s b

y GC/FID . d ) Tota l hydrocarbon s a s benzen e b y FID . e ) Moistur e conten t b y EPA standar dmethod . Sample s wer e collecte di ntedla r bag s utilizin g Teflo nsamplin g lines . Th e samplin g apparatu s wa s precleane d an d preteste d t o eliminat e aromati c backgroun d concentrations . Th e sample s wer e analyze d th e da y o f collectio nt o minimiz e sampl e degradation . Th e analysi s o f th e fue l gase s b y GC/FI D indicate d tha t a saturatio n effec t o f th e detecto r occurre dwhe nmor e tha n5 percen t tota l hydro carbon s wer e introduced . Thi s affecte d th e C.-C 6 

## syste m onl y an d methan e wa s th e componen t mos t affected . Fo r tha t reaso nmethan e (C x 

## ) wa s determine d b

y therma l conductivity . Fo r th e remainde r o f th e component sP. 4



### J 

# J-(2)AB0- X ^Flu e Ga s 

# L- l

Ho t 

# o n Heate r



# 0 ) 

# l o

Fue l Mi x AB I - X• Ethylbenzen e Uni t Of f - Natura l Ga s

ue l i Ni x1 ir w 1 

# Ga

s

(5 ) SH O - X Flu e Ga s 

# y^

Stea m Superheate r 

# I X - (3>W- « Fw 

## i Fro m Fue l Nix Dru

a



# Ga s
(4 ) 06 1 - XDehydrogenatlo nOf f - Ga s

Figur e 2-1 . Sampl e poin t schematic
.



# 2- 2P. 5



## thi s saturatio neffec t wa s remedie d b y dilutin g th e fue l sample s 100: 1 wit hnitroge nbefor e analysis . Th e dilution s wer e performe d o na rotamete r dilutio nboar dan

dth e result s wer e checke d b y using 0 2 

## , CH 4 

## , an

d H 2 

## a s interna l standard s whic hwer e verifie do nth e therma l conductivit y detector . Sinc e th e outle t sample s wer e o f lowe r concentrations , the y wer e injecte ddirectl y i nth e GC/FID . Th e previou s discussio nha s encompasse d th e overal l samplin g project . Th e followin g discussio nwil l concer nitsel f wit hth e individua l processes , th e stea m superheate r and th e oi l heater , respectively . 2. 1 STEA

M SUPERHEATE R Fiv e one-hour integrate dgra bsample s wer e take nsimultaneousl y a t eac ho f th e tw

o fue l inlet s an

d a t th e flu e ga s outlet . Ru non e a t th e superheate r outle t (SH0-1 ) wa s invali ddu e t o a leakin g bag . Eac hba g wa s analyze dfo r th e constituent s liste d i nSectio n2. 0 unde r (a)(b ) an d (c) . Prio r t o sampling , th e outle t o f th e superheate r wa s traverse d an d a sampl e extracte dandpumpe d t o th e continuou s FI D t o determin e i f ther e wer e an

y irregularitie s i nconcentration s o f tota l hydrocarbon s acros s th e stack . Th e result s exhibite d very lo w hydrocarbo nconcen tration s a t al l point s o f th e stack . Nois e level s o f th e monito r wer e highdu e t o th e vibration s o f th e stac k and mino r deviation s woul d hav e bee nhar dt o detect . Majo r deviation s (>1 0 percent ) woul d hav e bee n easil y detected , howeve r non e wer e detected . Th e G C analysi s summarie s ar e liste di nTable s 2- 1 throug h2-3 . Prio r t o eac hsamplin g run , a velocit y travers e anda moistur e determinatio nwer e conducte d a t th e outle t o f th e superheater . Thes e result s ar e liste d i nTabl e 2-4 . Th e superheate r operatin g condition s wer e no t alway s constant . Th e inle t ga s analysi s show s tha t th e benzen e level s droppe d a s testin g progressed . Thi s dat a i s no t i nconflic t wit hth e plan t proces s data . Th e outle t showe d<. 5 pp m benzen e o nal l test s whic hwoul d giv e high destructio nefficienc y result s o nal l th e tests . Th e benzen e emissio n dat a ar e summarize di nTabl e 2-7 .



# 2- 3

### P. 6

Tabl t 2-1 . SIMM YGA S ANALYSI S • OEHYDROGENATE D OFFGA S INLE T

A T E L PAS O PRODUCT S COMPANY , ODESSA . TEXA S

RU N NO . DAT E TIM E Specie s analysi s C-l * C- 2 • C . C- 3 C-4 C-5 C-6
Benzen e Toluen e Ethylbenztn e Xylen e Styren e TOTAL HYDROCARBON S b y specie s sianatio n

In*rts c H.O , Xb y volua e N. , Xb y volua e 0, , Xb y volut e CO. , Xb y volua e H. , Xb y volum e CH 4 , Xb y volua e TOTAL (X ) OG1- 1
ppa v a s coapound
27.55 0 742 46 2 2 8 <0. 1 <0. 1 5,04 7 29 9 4,27 8 <0. 1 <0. 1 38,40 6

_O.O d 4.5 6 .8 1 8.8 2 75.4 8 2.7 7 93.5 1 OGI- 2

pp- v a s coapound
25.39 0 S.65 9 321 18 <0. 1 <0. 1
4.38 0 25 3 3,54 5 <0. 1 <0. 1
39.56 6

.0. 0 3.9 6 .7 0 9.0 9 79.2 5 2.9 5 96.9 6 0GI- 3

pp- v a s coapound 26,55 0 69 1 444 3 6 <0. 1 <0. 1 2,20 7 13 6 7,46 4 <0. 1 <0. 1 37,52 8

•0. 0 7.1 6 .9 1 7.9 7 75.0 5 2.6 5 94.8 4 OGI- 4

ppav a s compound 32,47 0 5.10 4 35 3 2 1 <0. 1 <0. 1
2.43 2 7 8 1.54 1 <0. 1 <0. 1 41,99 9

BO. O 2.7 5 ND e 8.0 9 97.4 8 3.2 4 112.5 2 0GI- 5

ppav a s coapound 29,43 5 532 424 36 <0. 1 60 7 59 6 8 11 1 <0. 1 <0. 1
31.74 9

BO. O 4.7 7 .5 6 8.1 4 88.1 2 2.9 4 104.7 6 AVERAGE S

23,27 9 2,54 6 40 1 3 6 <0. 1 <0. 1 2,93 2 15 5 3,33 8 <0. 1 <0. 1 37,84 9

BO. O 4.6 4 .6 0 8.4 2 83.0 8 2.9 1 100.5 2
•Measure db

y a SMaadz uM1n1- 2 dua l GC/FI D usin g Porapa k Q coluan . b Heisure dby

a SMaadz uN1n1- 1 dua l GC/FI D usin g SP2100/0.1 XCartxwa xo n100/12 0 Suptlcopor t coluan . Steasurt db

y • Carl e 870 0 GC/TC O usin g Noltcula r Slav t andChroaosor b10 2 colutns . Ti.O Xno t atasurt dbu t assuae dt o b t dr y fo r rtportln g purposes . 'No t detected .



# 2- 4

### P. 7

Tabl e 2-2 . SUWAR YGA S ANALYSI S - FUE L GA S INLE T A T E L PAS O PRODUCT S COMPANY . OOESSA , TEXA S

• RU N NO . DAT E TIME Specie s analysi s
C-l ' C- 2 • C 2 C-3 C-4 C- 5 C-6
Benzen e Toluen e Ethylbenztn e Xylen e Styren e
TOTA L HYDROCARBON S b y specie s su_Mtio n

Inerts c H,0 , Xb y volua e N, , Xb y volua e 0- , Xb y volt—« CO. , Xb y volta e H- , Xb y volua e CH. , Xb y volia e CO , Xb y volua e TOTAL (X ) FGI- 1
ppav a s coapound 923,50 0 2,41 9 353 8 <0. 1 7
52 <0. 1 597 <0. 1 <0. 1
926,93 6

SO.O d 8.5 2 1.6 2 .28 ND « 92.3 5 .0 1 103.1 2 FGI- 2

ppav a s coapound 923,50 0 16,26 0 2,85 2 <0. 1 <0. 1 <0. 1
5 0 <0. 1 7 2 <0. 1 <0. 1
942,73 4

-0. 0 7.7 0 1.3 9 .4 1 N O 92.3 5 N D 103.7 7 FGI- 3

ppav a s coapound 854,70 0 16.79 9 26 0 37 2 3 9 <0. 1
15 2 <0. 1 <0. 1 <0. 1 <0. 1
872,32 2

80. 0 9.7 4 1.0 4 .4 1 N D 85.4 7 N D 98.4 2 FGI- 4

PP« v a s coapound 873,90 0 10.77 9 1,67 7 29 6 4 2 <0. 1
9. 1 <0. 1 <0. 1 <0. 1 <0. 1
876,70 3

80. 0 10.5 3 1.2 8 .4 5 N D 87.3 9 N D 100.9 3 FGI- S

ppav a s coapound 917,59 5 14,98 1 2,35 2 35 0 66 <0. 1
15. 7 <0. 1 <0. 1 <0. 1 <0. 1
935,36 3

-0. 0 4.7 2 .3 3 N D N D 91.7 6 N D 98.5 8 AVERAGE S

898,63 9
' 12,24 8 1,49 9 20 5 2 9 <0. 1
5 6 <0. 1 <0. 1 <0. 1 <0. 1
912,81 2

sO. O 8.2 4 1.1 3 .3 1 N D 89.8 6 N D 100.9 6
•Measure db

y a SMaadz uHini- 2 dua l GC/FI D usin g Porapa k Q coluan . •"Measure db y a SMaadz uMini- 1 dua l GC/FI D usin g SP2100/0.1 XCartowa xo n100/12 0 Suptlcopor t colusn . Steasurt dby

a Carl e 870 0 GC/TC O usin g Noltcula r Sitv t andChroaosor b10 2 coluans . Ti.O Xno t atasurt db

y assuae dt o b t dr y

fo r reportin g purposes . 'No t detected .



# 2-5 

# I

### P. 8

Tabl e 2-3 . SUWAR YGA S ANALYSI S - SUPERHEATE ROUTLE T A T E L PAS O PRODUCT S COMPANY , ODESSA , TEXA S

RU N NO . OAT E TIM E Specie s analysi s
C-l ' C- 2 • C 2 C- 3 C- 4 C* 5 C- 6
Benzene 0 Toluen e Ethylbenztn e Xylen e Styren e
TOTAL HYDROCARBON S b y specie s swaatio n

Inerts 0 H,0 , Xb y volua e N 2 , Xby volua e 0 2 , Xb y volua e CO, , Xb y volia e H, , Xb y volua e CH 4 , Xb y volua e TOTA L (X ) SHD- 1
ppav a s coapoun d b

~

—

- -

- -
—

—
• ~ SHO- 2

ppav a s coapound
2.6 4 0. 3 <0. 1 <0. 1 <0. 1 0. 2
0. 3 0. 3 <0. 1 <0. 1 <0. 1

3.7 4

6.2 8 82.3 4 3.1 5 10.6 9 ND * N O 102.4 6 SH0- 3

ppav a s coapound
5. 7 0. 4 <0. 1 <0. 1 <0. 1 <0. 1
0. 4 <0. 1 <0. 1 <0. 1 <0. 1

10. 7

6.4 5 77.8 1 4.6 1 9.1 2 N D N D 97.9 9 SHO- 4

ppav a s coapoun d
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1
<0. 1 4. 9 <0. 1 <0. 1 <0. 1

4. 9

5.4 2 86.5 0 6.6 0 9.1 0 N D N O 107.6 2 SHO- 5

ppav a s coapoun d
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1
<0. 1 6. 2 <0. 1 <0. 1 <0. 1

6. 2

5.6 0 76.3 0 7.6 0 7.7 0 N D N O 97.2 0 AVERAGE S

<0. 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1
<0. 1 3. 9 <0. 1 <0. 1 <0. 1

6. 4

5.9 4

9 1 5 N O NO 101.3 2

Runvoide ddu e t o leak

y bag . Steesure db

y a SMaadz uNinl- 1 dua l GC/FI D usin g SP2100/0.1 XCartowa xo n100/12 0 Suptlcopor t coluan . Steasurt db

y a Carl e 870 0 GCAC O using aoltcula r sitv t an dChroaosor b10 2 colians . *No t detected .



# 2-6

## Tabl e 2-4 . SUMMAR YMOISTUR E AN

D VOLUMETRI C FLOWRAT E - SUPERHEATER OUTLE T AT EL PAS O PRODUCT S COMPANY , ODESSA , TEXA S
Ru nno . Dat e Moistur e Volum e fractiondr

y ga s ( % b y volume ) ( M ) Volumetri c flowrat e (acfm ) (dscfm )

r o

«« j 

### SHO- 1 SHO- 2 SHO- 3 SHO- 4 SHO- 5 Average 9/27/7 9

9/28/7 9 9/29/7 9 10/02/7 9 10/03/7 9

— 15. 1

16. 9 17. 9 13. 5 14. 1 15. 5 

## .84 9 .83 1 .82 1 .86 3 .85 9 .84 5 85,26 3 95,83 6 83,26 9 97,09 4 86,66 3 89,62 5 34,01 2

37,43 9 32,05 3 39,43 6 34,59 6 35,50 7P.1 0

RU N NO . DAT E TIM E Specie s analysi s
C-l ' C- 2 • C 2 C- 3 C-4 C-5 C-6

Benzen e Toluen e Ethylbenzen e Xylen e Styren e
TOTAL HYDROCARBON S b y specie s suaaatio n

Inerts c H 2 0 , Xb y volua e N. , Xb y volua e 0, , Xb y volua e CO. , Xb y volua e H 2 > Xb y volua e CH 4 , Xb y volua e TOTAL (X ) Tabl e 2-5 . SUW1AR YGA S ANALYSI S OI L HEATE RINLE T AT E L PAS O PRODUCT S COMPANY , OOESSA , TEXA S

ABI- 2
ppa v a s coapound 925,15 5 21,46 2 8,56 0 291 5 6 <0. 1
57. 4 23. 5 <0. 1 <0. 1 <0. 1
955,60 5



### -o.o d 6.7 9 0.7 1 0.3 1 ND « 92.5 2 103.3 7 ABI- 3

ppa v a s coapound 897,18 0 33,40 4 5,50 8 <0. 1 <0. 1 4 0
65. 7 3. 8 <0. 1 71. 5 <0. 1
937,27 3

"0. 0 4.2 7 0.0 2 0.1 4 N D 89.7 2 98.0 6 ABI- 4

ppa v a s coapound
944.78 5 12.46 7 1,74 4 29 7 4 7 <0. 1
55. 8 3. 2 83. 4 <0. 1 <0. 1
959,48 2

"0. 0 4.5 4 0.3 6 0.7 4 N D 94.4 8 101.5 9 AVERAGE S

ppa v a s coapound 922,37 3 22,44 4 5,27 1 19 6 3 4 4 0
59. 6 10. 2 83. 4 71. 5 <0. 1
950,45 2

"0. 0 5.2 0 0.3 6 0.4 0 N D 92.2 4 101.0 0 Steasurt d b

y a Shiaadz u Mini- 2 dua l GC/FI D usin g Porapa k Q coliam . Steasurt d b

y a Shiaadz u Mini- 1 dua l GC/FI D usin g SP2100/0.1 X Carbowa x on.100/12 0 Suptlcoport coluan . Steasurt d b

y a Carl e 8700 GC/TC

O usin g Noltcula r Sitv t an d Chroaosorb 10

2 coluans . StJS C no t atasurt d b

y assuae d t o b e dr y fo r reportin g purposes . So t detected .



## 2- 8P.1 1 

# q

Tabl e 2-6 . SUMMAR YGAS ANALYSI S OI L BURNE R OUTLE TA T E L PAS O PRODUCTS COMPANY , ODESSA , TEXA S

RU N NO . DAT E TIN E Specie s analysi s
C-l ' C- 2 • C 2 C- 3 C-4 C-5 C-6
Benzen e Toluen e Ethylbenzen e Xylen e Styren e
TOTAL HYDROCARBON S b y specie s staaatio n

Inerts c H 2 0 . Xb y volta e N 2 . Xb y volua e 0, , Xb y volua e CO- , Xb y volw e H 2 , Xb y volia * CH 4 , Xb y volua e TOTAL (X ) AB0- 2
ppav a s coapound
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1 1. 3 <0. 1 <0. 1 <0. 1 <0. 1

1. 3

5.5 3 75.8 1 4.6 1 9.8 9 W d N D 95.3 9 ABO- 3

ppav a s coapound
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1

<0. 1

6.4 5 76.9 4 3.6 3 10.3 7 N D N D 97.3 9 AB0- 4

ppav a s coapound
<.0 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1

<0. 1

6.3 4 73.9 7 3.9 8 9.5 0 N D N O 93.6 9 AVERAG E

Ppav a s coapound
<0. 1 <0. 1 <0. 1 <0. 1 <0. 1 <0. 1
0.4 3 <0. 1 <0. 1 <0. 1 <0. 1

0.4 3

6.0 7 75.5 7 3.9 2 9.9 2 N O N O 95.4 9 Steasurt d b

y a Shiaadz u Nlnl- 2 dua l GC/FI D usin g Porapa k Q coltan . Steasurt d b

y a Shiaadz u Ninl- 1 dua l GC/FI D usin g SP2100/0.1 X Carbowa x e n 100/12 0 Si^elcopor t coluan . Steasurt d b

y a Cari t 870 0 GC/TC

D usin g Noltcula r Slave an d Chroaosorb 10 2 colians . Slo t detected .


# I 2- 9P.1 2 

# i

i i i i i i i i i
ft 

# fr fr No problem s wer e encountere ddurin g th e samplin g usin g th e modifie d

EP A 11 0 samplin g procedur e (se e Sectio n4) . No problem s wer e encountere d i nth e analytica l procedures . Th e procedure s ar e als o explaine di n Sectio n4 . 2. 2 OI L HEATE R Thre e one-hou r integrate dba g sample s wer e take na t th e fue l inle t an dth e outle t t o th e oi l heate r simultaneously . Eac hba g wa s analyze d fo r (a) , (b ) an

d(c) , liste di nSectio n2.0 . Durin g th e tes t perio da fina l scrubbe r i nth e ethy l benzen e uni t wa s cleane dan dthi s resulte d i n a lo w benzen e concentratio ni nth e fue l gas . Th e result s ar e presente d i nTabl e 2.5 . Tabl e 2. 6 show s th e result s o f th e sample s obtaine da t th e outle t o f th e oi l heater . Dilutio nratio s wer e calculate dusin g stoichiometri c combustio ncalculations . Th e resultan t dilutio nratio s wer e the napplie d t o th e benzen e inle t andoutle t concentration s t o giv e th e boile r benzen e reductio nefficienc y (se e Tabl e 2.7) . Ru nAB- 2 appear s t o hav e a poo r efficiency ; however , thi s i s cause db y th e lo w benzen e concentratio ni nth e fuel . No samplin g o r analytica l problem s wer e encountered . No velocit y travers e o r moistur e dat a wer e obtaine d a t th e outle t a s th e samplin g poin t wa s inaccessable .

2-1 0

### Tabl e 2-7 . SUMMAR Y- BENZEN E REMOVAL EFFICIENC YA T E L PAS O PRODUCT S COMPANY ,

ODESSA , TEXA S

Ru nno .
A80- 2 ABO- 3 ABO- 4 SHO- 2 SHO- 3 SHO- 4 SHO- 5 Benzen e concentratio n

Stac k outle t (ppa v w e


### 1. 3 <0. 1 <0. 1 

### 0. 3 0. 4 <0. 1 <0. 1 

### t ) (ppia

v dry , 

### MX0_ ) 1.5 2 <0. 1 <0. 1 

### .3 3 .4 9 <0. 1 <0. 1 Fue l Inle t

(ppmv )

57. 4 65. 7 55. 8 I/O 6 

### I/ O I/ O 1/ 0 0x



### yfl ' ( Xb y volume
4.1 6 3.6 3 3.9 8 3.1 5 4.6 1 

### 6. 6 7. 6 • nconcentratio n Stac k wet ) ( Xby

volun e dry )
4.4 0 3.8 8 4.2 4 3.3 6 4.9 3 6.9 8 8.0 5 Moistur e

stack 8 

### (X )

5.5 3 6.4 5 6.2 4 6.2 8 6.4 5 5.4 2 5.6 0 Dilutio n

facto r

10.0 1 9.4 8 10.3 7 

### I/ O I/ O I/ D I/ O Benzen e remova l

efficienc y 

### (X )
73.4 9 "10 0 "10 0 

### I/ O I/ D "10 0 "10 0 Emlssl o

rate s (lb/hr ) 

### I/ O I/ O I/ O .1 6 .1 7 <.05 2 <.04 5 

### n (kg/hr ) 

### I/ O I/ O I/ O .07 .0 8 <.0 2 <.0 2

r o i a 

### A s analyze dI nsample . b 

### I/ D - Insufficien t data .