P.1 

OAR Box 1870 

Prepped by Ollie Stewart 

Document Number: 

15) ll-A-20 

Docket Number: 

A-90-19 

Printed 11/28/2008 7:05:04 AM Sheet 15 of 67 
P.2 

',>• 

SER& 

m\- _i. .tr . **-?-» 4 i 

United States Office of Air Quality 

Environmental Protection Planning and Standards 

Agency Research Triangle "--' 

Air 

n A-90-19 Benzene n.A-2o 

Organic Chemiuc. 

Manufacturing 

Ethylbenzene/Styrene 

EMB Report 79-OCM-15 

April 1981 

Emission Test Report 

El Paso Products 

Company 

Odessa, Texas 

l!) 00 

IMJ 1 W E 

SEP I •( 1992 

EPA AIR DOCKET 

I 

I 

I 

I 
P.3 

2.0 SUMMARY AND DISCUSSION RESULTS 

The sampling and analysis data at El Paso Products were obtained 

from two separate process locations. The first week was spent sampling 

and analyzing the fuel and the outlet gases from the steam superheater. 

The second week was spent collecting data from the fuel gas inlet and 

the exhaust gases of the hot oil heater. The hot oil heater and the 

steam superheater are diagrammed in Figure 2-1. Points one and two were 

sampled simultaneously and points three, four and five were sampled 

simultaneously in order to determine the benzene destruction efficiency 

of the combustion processes. Figure 2-1 shows the sampling designations 

next to the sampling point number. Samples were analyzed for: 

a) C02, 02 , N2, H2, CH4 by GC/TCD. 

b) Benzene, toluene, xylene, ethylbenzene, styrene 

by GC/FID. 

c) Low molecular weight hydrocarbons as C_-C6 

species by GC/FID. 

d) Total hydrocarbons as benzene by FID. 

e) Moisture content by EPA standard method. 

Samples were collected in tedlar bags utilizing Teflon sampling 

lines. The sampling apparatus was precleaned and pretested to eliminate 

aromatic background concentrations. The samples were analyzed the day 

of collection to minimize sample degradation. 

The analysis of the fuel gases by GC/FID indicated that a saturation 

effect of the detector occurred when more than 5 percent total hydrocarbons were introduced. This affected the C.-C6 system only and methane 

was the component most affected. For that reason methane (Cx) was 

determined by thermal conductivity. For the remainder of the components 
P.4 

J 

J-(2)AB0-X 

^Flu e Gas 

L-l 

Hot 

on 

Heater 

0) 

l o 

Fuel Mix 

ABI - X • 

Ethylbenzene Unit Off -

Natural Gas 

uel i 

Nix 1 

irw 1 

Gas 

(5) SHO - X 

Flue Gas 

y^ 

Steam 

Superheater 

I X - (3>W- « Fw i 

From Fuel Nix Drua 

Gas 

(4) 061 - X Dehydrogenatlon Off - Gas 

Figure 2-1. Sample point schematic. 

2-2 
P.5 

this saturation effect was remedied by diluting the fuel samples 100:1 

with nitrogen before analysis. The dilutions were performed on a rotameter 

dilution board and the results were checked by using 02 , CH4, and H2 as 

internal standards which were verified on the thermal conductivity 

detector. Since the outlet samples were of lower concentrations, they 

were injected directly in the GC/FID. 

The previous discussion has encompassed the overall sampling project. 

The following discussion will concern itself with the individual processes, 

the steam superheater and the oil heater, respectively. 

2.1 STEAM SUPERHEATER 

Five one-hour integrated grab samples were taken simultaneously at 

each of the two fuel inlets and at the flue gas outlet. Run one at the 

superheater outlet (SH0-1) was invalid due to a leaking bag. Each bag 

was analyzed for the constituents listed in Section 2.0 under (a)(b) and 

(c). 

Prior to sampling, the outlet of the superheater was traversed and 

a sample extracted and pumped to the continuous FID to determine if 

there were any irregularities in concentrations of total hydrocarbons 

across the stack. The results exhibited very low hydrocarbon concentrations at all points of the stack. Noise levels of the monitor were 

high due to the vibrations of the stack and minor deviations would have 

been hard to detect. Major deviations (>10 percent) would have been 

easily detected, however none were detected. The GC analysis summaries 

are listed in Tables 2-1 through 2-3. Prior to each sampling run, a 

velocity traverse and a moisture determination were conducted at the 

outlet of the superheater. These results are listed in Table 2-4. 

The superheater operating conditions were not always constant. The 

inlet gas analysis shows that the benzene levels dropped as testing 

progressed. This data is not in conflict with the plant process data. 

The outlet showed <.5 ppm benzene on all tests which would give high 

destruction efficiency results on all the tests. The benzene emission 

data are summarized in Table 2-7. 

2-3 
P.6 

Tablt 2-1. SIMM Y GAS ANALYSIS • OEHYDROGENATED OFFGAS INLET 

AT EL PASO PRODUCTS COMPANY, ODESSA. TEXAS 

RUN NO. 

DATE 

TIME 

Species 

analysis 

C-l* 

C-2 • C. 

C-3 

C-4 

C-5 

C-6 

Benzene 

Toluene 

Ethylbenztne 

Xylene 

Styrene 

TOTAL 

HYDROCARBONS 

by species 

sianation 

In*rtsc 

H.O, X by voluae 

N., X by voluae 

0,, X by volute 

CO., X by voluae 

H., X by volume 

CH4, X by voluae 

TOTAL (X) 

OG1-1 

ppav as 

coapound 

27.550 

742 

462 

28 

<0.1 

<0.1 

5,047 

299 

4,278 

<0.1 

<0.1 

38,406 

_O.Od 

4.56 

.81 

8.82 

75.48 

2.77 

93.51 

OGI-2 

pp-v as 

coapound 

25.390 

S.659 

321 

18 

<0.1 

<0.1 

4.380 

253 

3,545 

<0.1 

<0.1 

39.566 

.0.0 

3.96 

.70 

9.09 

79.25 

2.95 

96.96 

0GI-3 

pp-v as 

coapound 

26,550 

691 

444 

36 

<0.1 

<0.1 

2,207 

136 

7,464 

<0.1 

<0.1 

37,528 

•0.0 

7.16 

.91 

7.97 

75.05 

2.65 

94.84 

OGI-4 

ppav as 

compound 

32,470 

5.104 

353 

21 

<0.1 

<0.1 

2.432 

78 

1.541 

<0.1 

<0.1 

41,999 

BO.O 

2.75 

NDe 

8.09 

97.48 

3.24 

112.52 

0GI-5 

ppav as 

coapound 

29,435 

532 

424 

36 

<0.1 

607 

596 

8 

111 

<0.1 

<0.1 

31.749 

BO.O 

4.77 

.56 

8.14 

88.12 

2.94 

104.76 

AVERAGES 

23,279 

2,546 

401 

36 

<0.1 

<0.1 

2,932 

155 

3,338 

<0.1 

<0.1 

37,849 

BO.O 

4.64 

.60 

8.42 

83.08 

2.91 

100.52 

•Measured by a SMaadzu M1n1-2 dual GC/FID using Porapak Q coluan. 

bHeisured by a SMaadzu N1n1-1 dual GC/FID using SP2100/0.1X Cartxwax on 100/120 Suptlcoport coluan. 

Steasurtd by • Carle 8700 GC/TCO using Noltcular Slavt and Chroaosorb 102 colutns. 

Ti.OX not atasurtd but assuaed to bt dry for rtportlng purposes. 

'Not detected. 

2-4 
P.7 

Table 2-2. SUWARY GAS ANALYSIS - FUEL GAS INLET 

AT EL PASO PRODUCTS COMPANY. OOESSA, TEXAS 

• RUN NO. 

DATE 

TIME 

Species 

analysis 

C-l' 

C-2 • C2 

C-3 

C-4 

C-5 

C-6 

Benzene 

Toluene 

Ethylbenztne 

Xylene 

Styrene 

TOTAL 

HYDROCARBONS 

by species 

su_Mtion 

Inertsc 

H,0, X by voluae 

N,, X by voluae 

0-, X by volt—« 

CO., X by voltae 

H-, X by voluae 

CH., X by voliae 

CO, X by voluae 

TOTAL (X) 

FGI-1 

ppav as 

coapound 

923,500 

2,419 

353 

8 

<0.1 

7 

52 

<0.1 

597 

<0.1 

<0.1 

926,936 

SO.Od 

8.52 

1.62 

.28 

ND« 

92.35 

.01 

103.12 

FGI-2 

ppav as 

coapound 

923,500 

16,260 

2,852 

<0.1 

<0.1 

<0.1 

50 

<0.1 

72 

<0.1 

<0.1 

942,734 

-0.0 

7.70 

1.39 

.41 

NO 

92.35 

ND 

103.77 

FGI-3 

ppav as 

coapound 

854,700 

16.799 

260 

372 

39 

<0.1 

152 

<0.1 

<0.1 

<0.1 

<0.1 

872,322 

80.0 

9.74 

1.04 

.41 

ND 

85.47 

ND 

98.42 

FGI-4 

PP«v as 

coapound 

873,900 

10.779 

1,677 

296 

42 

<0.1 

9.1 

<0.1 

<0.1 

<0.1 

<0.1 

876,703 

80.0 

10.53 

1.28 

.45 

ND 

87.39 

ND 

100.93 

FGI-S 

ppav as 

coapound 

917,595 

14,981 

2,352 

350 

66 

<0.1 

15.7 

<0.1 

<0.1 

<0.1 

<0.1 

935,363 

-0.0 

4.72 

.33 

ND 

ND 

91.76 

ND 

98.58 

AVERAGES 

898,639 

' 12,248 

1,499 

205 

29 

<0.1 

56 

<0.1 

<0.1 

<0.1 

<0.1 

912,812 

sO.O 

8.24 

1.13 

.31 

ND 

89.86 

ND 

100.96 

•Measured by a SMaadzu Hini-2 dual GC/FID using Porapak Q coluan. 

•"Measured by a SMaadzu Mini-1 dual GC/FID using SP2100/0.1X Cartowax on 100/120 Suptlcoport colusn. 

Steasurtd by a Carle 8700 GC/TCO using Noltcular Sitvt and Chroaosorb 102 coluans. 

Ti.OX not atasurtd by assuaed to bt dry for reporting purposes. 

'Not detected. 

2-5 

I 
P.8 

Table 2-3. SUWARY GAS ANALYSIS - SUPERHEATER OUTLET AT 

EL PASO PRODUCTS COMPANY, ODESSA, TEXAS 

RUN NO. 

OATE 

TIME 

Species 

analysis 

C-l' 

C-2 • C2 

C-3 

C-4 

C*5 

C-6 

Benzene0 

Toluene 

Ethylbenztne 

Xylene 

Styrene 

TOTAL 

HYDROCARBONS 

by species 

swaation 

Inerts0 

H,0, X by voluae 

N2, X by voluae 

02 , X by voluae 

CO,, X by voliae 

H,, X by voluae 

CH4, X by voluae 

TOTAL (X) 

SHD-1 

ppav as 

coapound 

b 

~ 

— 

--

--

— 

— 

•~ 

SHO-2 

ppav as 

coapound 

2.64 

0.3 

<0.1 

<0.1 

<0.1 

0.2 

0.3 

0.3 

<0.1 

<0.1 

<0.1 

3.74 

6.28 

82.34 

3.15 

10.69 

ND* 

NO 

102.46 

SH0-3 

ppav as 

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 

6.45 

77.81 

4.61 

9.12 

ND 

ND 

97.99 

SHO-4 

ppav as 

coapound 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

4.9 

<0.1 

<0.1 

<0.1 

4.9 

5.42 

86.50 

6.60 

9.10 

ND 

NO 

107.62 

SHO-5 

ppav as 

coapound 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6.2 

<0.1 

<0.1 

<0.1 

6.2 

5.60 

76.30 

7.60 

7.70 

ND 

NO 

97.20 

AVERAGES 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

3.9 

<0.1 

<0.1 

<0.1 

6.4 

5.94 

9 15 

NO 

NO 

101.32 

Run voided due to leaky bag. 

Steesured by a SMaadzu Ninl-1 dual GC/FID using SP2100/0.1X Cartowax on 100/120 Suptlcoport coluan. 

Steasurtd by a Carle 8700 GCACO using aoltcular sitvt and Chroaosorb 102 colians. 

*Not detected. 

2-6 
Table 2-4. SUMMARY MOISTURE AND VOLUMETRIC FLOWRATE - SUPERHEATER 

OUTLET AT EL PASO PRODUCTS COMPANY, ODESSA, TEXAS 

Run no. Date Moisture Volume fraction dry gas 

(% by volume) (M ) 

Volumetric flowrate 

(acfm) (dscfm) 

ro 

««j 

SHO-1 

SHO-2 

SHO-3 

SHO-4 

SHO-5 

Average 

9/27/79 

9/28/79 

9/29/79 

10/02/79 

10/03/79 

— 

15.1 

16.9 

17.9 

13.5 

14.1 

15.5 

.849 

.831 

.821 

.863 

.859 

.845 

85,263 

95,836 

83,269 

97,094 

86,663 

89,625 

34,012 

37,439 

32,053 

39,436 

34,596 

35,507 
P.10 

RUN NO. 

DATE 

TIME 

Species 

analysis 

C-l' 

C-2 • C2 

C-3 

C-4 

C-5 

C-6 

Benzene 

Toluene 

Ethylbenzene 

Xylene 

Styrene 

TOTAL 

HYDROCARBONS 

by species 

suaaation 

Inertsc 

H20, X by voluae 

N., X by voluae 

0,, X by voluae 

CO., X by voluae 

H2> X by voluae 

CH4, X by voluae 

TOTAL (X) 

Table 2-5. SUW1ARY GAS ANALYSIS OIL HEATER INLET AT EL PASO 

PRODUCTS COMPANY, OOESSA, TEXAS 

ABI-2 

ppav as 

coapound 

925,155 

21,462 

8,560 

291 

56 

<0.1 

57.4 

23.5 

<0.1 

<0.1 

<0.1 

955,605 

-o.od 

6.79 

0.71 

0.31 

ND« 

92.52 

103.37 

ABI-3 

ppav as 

coapound 

897,180 

33,404 

5,508 

<0.1 

<0.1 

40 

65.7 

3.8 

<0.1 

71.5 

<0.1 

937,273 

"0.0 

4.27 

0.02 

0.14 

ND 

89.72 

98.06 

ABI-4 

ppav as 

coapound 

944.785 

12.467 

1,744 

297 

47 

<0.1 

55.8 

3.2 

83.4 

<0.1 

<0.1 

959,482 

"0.0 

4.54 

0.36 

0.74 

ND 

94.48 

101.59 

AVERAGES 

ppav as 

coapound 

922,373 

22,444 

5,271 

196 

34 

40 

59.6 

10.2 

83.4 

71.5 

<0.1 

950,452 

"0.0 

5.20 

0.36 

0.40 

ND 

92.24 

101.00 

Steasurtd by a Shiaadzu Mini-2 dual GC/FID using Porapak Q coliam. 

Steasurtd by a Shiaadzu Mini-1 dual GC/FID using SP2100/0.1X Carbowax 

on.100/120 Suptlcoport coluan. 

Steasurtd by a Carle 8700 GC/TCO using Noltcular Sitvt and Chroaosorb 102 coluans. 

StJSC not atasurtd by assuaed to be dry for reporting purposes. 

Sot detected. 

2-8 
P.11 

q 

Tabl e 2-6 . SUMMARY GAS ANALYSIS OIL BURNER OUTLET AT 

EL PASO PRODUCTS COMPANY, ODESSA, TEXAS 

RUN NO. 

DATE 

TINE 

Species 

analysis 

C-l' 

C-2 • C2 

C-3 

C-4 

C-5 

C-6 

Benzene 

Toluene 

Ethylbenzene 

Xylene 

Styrene 

TOTAL 

HYDROCARBONS 

by species 

staaation 

Inertsc 

H20. X by voltae 

N2. X by voluae 

0,, X by voluae 

CO-, X by volwe 

H2, X by volia* 

CH4, X by voluae 

TOTAL (X) 

AB0-2 

ppav as 

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 

5.53 

75.81 

4.61 

9.89 

W

d 

ND 

95.39 

ABO-3 

ppav as 

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 

6.45 

76.94 

3.63 

10.37 

ND 

ND 

97.39 

AB0-4 

ppav as 

coapound 

<.01 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

6.34 

73.97 

3.98 

9.50 

ND 

NO 

93.69 

AVERAGE 

Ppav as 

coapound 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.43 

<0.1 

<0.1 

<0.1 

<0.1 

0.43 

6.07 

75.57 

3.92 

9.92 

NO 

NO 

95.49 

Steasurtd by a Shiaadzu Nlnl-2 dual GC/FID using Porapak Q coltan. 

Steasurtd by a Shiaadzu Ninl-1 dual GC/FID using SP2100/0.1X Carbowax 

en 100/120 Si^elcoport coluan. 

Steasurtd by a Carit 8700 GC/TCD using Noltcular Slave and Chroaosorb 102 colians. 

Slot detected. 

I 

2-9 
P.12 

i 

i 

i 

i 

i 

i 

i 

i 

i 

i 

ft 

fr 

fr 

No problems were encountered during the sampling using the modified 

EPA 110 sampling procedure (see Section 4). No problems were encountered 

in the analytical procedures. The procedures are also explained in 

Section 4. 

2.2 OIL HEATER 

Three one-hour integrated bag samples were taken at the fuel inlet 

and the outlet to the oil heater simultaneously. Each bag was analyzed 

for (a), (b) and (c), listed in Section 2.0. During the test period a 

final scrubber in the ethyl benzene unit was cleaned and this resulted in 

a low benzene concentration in the fuel gas. The results are presented 

in Table 2.5. Table 2.6 shows the results of the samples obtained at 

the outlet of the oil heater. Dilution ratios were calculated using 

stoichiometric combustion calculations. The resultant dilution ratios 

were then applied to the benzene inlet and outlet concentrations to give 

the boiler benzene reduction efficiency (see Table 2.7). Run AB-2 

appears to have a poor efficiency; however, this is caused by the low 

benzene concentration in the fuel. No sampling or analytical problems 

were encountered. No velocity traverse or moisture data were obtained 

at the outlet as the sampling point was inaccessable. 

2-10 
Table 2-7. SUMMARY - BENZENE REMOVAL EFFICIENCY AT EL PASO PRODUCTS COMPANY, 

ODESSA, TEXAS 

Run no. 

A80-2 

ABO-3 

ABO-4 

SHO-2 

SHO-3 

SHO-4 

SHO-5 

Benzene concentration 

Stack outlet 

(ppav we 

1.3 

<0.1 

<0.1 

0.3 

0.4 

<0.1 

<0.1 

t) (ppiav dry, 

MX0_) 

1.52 

<0.1 

<0.1 

.33 

.49 

<0.1 

<0.1 

Fuel Inlet 

(ppmv) 

57.4 

65.7 

55.8 

I/O6 

I/O 

I/O 

1/0 

0xyfl' 

(X by volume 

4.16 

3.63 

3.98 

3.15 

4.61 

6.6 

7.6 

•n concentration 

Stack 

wet) (X by volune dry) 

4.40 

3.88 

4.24 

3.36 

4.93 

6.98 

8.05 

Moisture 

stack8 

(X) 

5.53 

6.45 

6.24 

6.28 

6.45 

5.42 

5.60 

Dilution 

factor 

10.01 

9.48 

10.37 

I/O 

I/O 

I/D 

I/O 

Benzene removal 

efficiency 

(X) 

73.49 

"100 

"100 

I/O 

I/D 

"100 

"100 

Emlsslo 

rates 

(lb/hr) 

I/O 

I/O 

I/O 

.16 

.17 

<.052 

<.045 

n 

(kg/hr) 

I/O 

I/O 

I/O 

.07 

.08 

<.02 

<.02 

ro 

i 

aAs analyzed In sample. 

bI/D - Insufficient data.