OAR Box 1870 

Prepped by Ollie Stewart 

Document Number: 

12) ll-A-17 

Docket Number: 

A-90-19 

Printed 11/28/2008 7:05:04 AM Sheet 12 of 67 

P.1 
P.2 

-»ER-\ 

United States 

Environmental Protection 

Agency 

Office of Air Quality 

Planning and Standards 

Research Triangle P ' 

EMB Report 80-OCM-19 

August 1980 

Air A-90-19 

ll-A-17 Benzene 

Organic Chemical 

Manufacturing 

Ethylbenzene/Styrene 

Emission Test Repo 

USS Chemicals 

Houston, Texas 
P.3 

2. SUMMARY AND DISCUSSION OF RESULTS 

2.1 GAS ANALYSIS RESULTS 

The sampling and analysis data at USSC Houston were obtained from 

five locations within the ethylbenzene/styrene facility. The first phase 

involved the sampling and analysis of the gas stream composition at the 

reboiler stack outlet, the superheater stack outlet, and the combined gas 

inlet to the reboiler and superheater. The second phase involved sampling 

and analysis at two column vent locations. These locations were the 

styrene finishing column vent to the atmosphere and the combined hotwell 

vent recovery system prior to the natural gas ejector. 

During the first phase of testing, the three locations were sampled 

simultaneously in order to determine the benzene mass removal efficiency 

of the combustion processes in addition to the benzene emission 

concentrations. 

Summaries of the results of testing are presented in Tables 2-1 

through 2-3. The average benzene emission results and removal efficiencies 

are summarized in Table 2-4. The benzene emission concentrations from 

the two heaters ranged from <0.1 to 0.34 ppmv. The average benzene 

concentration in the fuel gas was 440 ppm. Using these results in a 

combustion calculation (described in Appendix A) yields benzene removal 

efficiencies ranging from 99.4 to 99.8 percent. The results are consistent 

from run to run and there were no known sampling or process difficulties 

during these tests. 

The results of testing at the styrene column vent are presented in 

Table 2-5. During sampling, condensate was observed in the sample line. 

A sample of this liquid was analyzed and found to be essentially styrene. 

No attempt was made to estimate the condensate volume or mass rate. 

2-1 
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Table 2-2. REBOILER STACK OUTLET GAS ANALYSIS RESULTS AT USSC-HOUSTON 

RUN NO. 

DATE 

TIME 

RBO-1 

6/24/80 

0960 HRS 

RB0-2 

6/25/80 

1000 HRS 

RBO-3 

6/25/80 

1400 HRS 

AVERAGE 

Species analysis 

Retention 

tine (min) 

ppmv as 

conpound 

ppmv as 

benzene 

ppmv as 

compound 

ppmv as 

benzene 

ppmv as 

compound 

ppmv as 

benzene 

ppmv as 

compound 

ppmv as 

benzene 

C-la 

C-2 

C-3 

C-4 

C-5 

C-6C 

Benzene 

Toluene 

Ethylbenzene 

Styrene 

0.95 

1.33 

1.97 

3.41 

6.49 

2.13 

3.16 

4.82 

7.29 

8.3 

Total hydrocarbons 

by species 

summation 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.394 

0.394 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.450 

0.450 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.063 

0.322 

0.385 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.092 

0.368 

0.460 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.345 

0.324 

0.470 

0.526 

1.67 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.345 

0.399 

0.683 

0.601 

2.03 

NDb 

ND 

ND 

ND 

ND 

ND 

0.115 

0.108 

0.178 

0.414 

0.815 

ND 

ND 

ND 

ND 

ND 

ND 

0.115 

0.133 

0.258 

0.473 

0.979 

Inerts 

H20 X by volume6 

C02 X by volume 

CO X by volume 

N2 X by volume 

02 X by volume 

H2 X by volume 

CH4 X by volume 

TOTAL (X) 

~ 5.0 

12.43 

< 0.1 

85.98 

3.91 

< 0.1 

< 0.1 

107.3 

Porapak Q column. 

Not determined. 

CSP2100/0.1X Carbowax on 100/120 Supelcoport column. 

Stolecular Sieve and Chromsorb 102.columns. 

e H2 0 X by volume - saturated at analysis temperature 92°F. 

~ 

< 

< 

< 

5.0 

9.81 

0.1 

83.26 

3.55 

0.1 

0.1 

101.6 

~ 5.0 

9.81 

< 0.1 

83.10 

3.17 

< 0.1 

< 0.1 

101.1 

-

< 

< 

< 

5 0 

10.6 

0 

84 

3 

0 

0. 

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11 

54 

1 

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103.3 
RUN NO. 

DATE 

TIHE .'*• • 

Retention 

Species analysis time (min) 

C-la 

C-2 

C-3 

C-4 

C-5 

C-6C 

'i* Benzene 

Toluene 

Unknown 

Styrene 

0.95 

1.33 

1.97 

3.41 

6.49 

2.13 

3.51 

4.80 

8.16 

9.30 

Total hydrocarbons 

by species 

summation 

Inerts 

H20, X by volume6 

N2, X by volume 

Oj, X by volume 

C02, X by volume 

TOTAL (X) 

aPorapak Q column. 

Not determined. 

CSP2100/0.1X Carbowax on 100/120 

ecular Sieve and Chromosorb 

e H2 0 X by volume - saturated at 

Table 2-3. 

SHO-1 

6/24/80 

0900 HRS 

ppmv as 

compound 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.20 

<0.1 

<0.1 

<0.1 

<0.1 

0.20 

Supelcoport 

102 columns. 

~5.00e 

85.95 

5.96 

11.02 

107.93 

column 

SUPERHEATER STACK OUTLET GAS ANALYSIS RESULTS AT USSC-HOUSTON 

ppmv as 

benzene 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.237 

<0.1 

<0.1 

<0.1 

<0.1 

0.237 

. 

analysis temperature 92°F. 

SHO-2 

6/25/80 

1000 HRS 

ppmv as 

compound 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.163 

0.432 

0.632 

1.13 

2.36 

-5.00 

82.82 

6.90 

7.93 

102.65 

ppmv as 

benzene 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.163 

0.532 

0.949 

1.29 

2.93 

SH0-3 

6/25/80 

1400 HRS 

ppmv as 

compound 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.195 

0.220 

0.099 

0.134 

0.648 

ppmv as 

benzene 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

<0.1 

0.195 

0.271 

0.144 

0.153 

0.763 

-5.00 

83.10 

5.62 

9.39 

103.11 

ppmv as 

compound 

NDb 

ND 

ND 

ND 

ND 

0.067 

0.119 

0.217 

0.260 

0.428 

1.09 

-

AVERAGE 

ppmv as 

benzene 

NO 

ND 

ND 

NO 

ND 

0.079 

0.119 

0.268 

0.364 

0.481 

1.31 

5.00 

83.96 

6.16 

9:45 

104.56 

» 

.* . 
ro 

tn 

• • • I 

Table 2-4. SUMMARY BENZENE REMOVAL EFFICIENCY 

b e d Benzene 

Oxygen Benzene Benzene emissions Benzene inlet Dilution Removal 

(X v/v dry) (ppm wet) (ppmv 9 3% 02 dry) (ppmv) Factor Efficiency9 

Run 

Number 

RBO-1 

RB0-2 

RB0-3 

SHO-1 

SH0-2 

SHO-3 

Moisture 

(X) 

5.0 

5.0 

5.0 

5.0 

5.0 

5.0 

3.91 

3.55 

3.17 

5.96 

6.90 

5.62 

<0.1 

<0.1 

0.345 

<0.1 

0.163 

0.195 

<0.1 

<0.1 

0.366 

<0.1 

0.219 

0.240 

421 

425 

491 

421 

425 

491 

8.73 

8.41 

8.36 

9.79 

10.33 

9.61 

99.8 

99.8 

99.4 

99.8 

99.6 

99.6 

Saturated at 92°-analyt1cal temperature. 

Determined by TCD analysis. 

cAt stack conditions. 

Equation A.3 

eSee Table 2-1, Combined Gas Inlet (CGI). 

See Appendix A - Table A-l. 

"Equation A.4. 

-o 

* ^ i 
• auie t-o. ounciic rii-USHING COLUMN VENT GAS ANALYSIS RESULTS AT USSC-HOUSTON 

RUN NO. 

DATE 

TIME 

SFCV-1 

6/26/80 

SFCV-2 

6/26/80 

SFCV-3 

6/26/80 AVERAGE 

Species 

C-la 

C-2 

C-3 

C-4 

C-4 

C-5 

C-5 

analysis 

Retention 

time (min) 

0.97 

1.37 

2.20 

3.60 

4.10 

7.64 

8.44 

ppmv as 

compound 

126,466 

4,157 

1,254 

147 

249 

68.2 

61.2 

ppmv as 

benzene 

29,720 

1,833 

803 

112 

189 * 

67.2 

60.3 

ppmv as 

compound 

134,413 

4,421 

1,199 

145 

240 

64.9 

57.1 

ppmv as 

benzene 

31,587 

1,950 

767 

110 

183 

63.9 

56.2 

ppmv as 

compound 

141,213 

4,149 

1,229 

139 

245 

68.9 

56.0 

ppmv as 

benzene 

33,185 

1,830 

786 

106 

187 

67.9 

56.2 

ppmv as 

compound 

134,031 

4,242 

1,227 

144 

245 

67.3 

58.1 

ppmv as 

benzene 

31,497 

1,871 

785 

109 

186 

66.3 

57.6 

C-6" 

C-6 

Benzene 

Unknown 

Unknown 

Toluene 

Unknown 

Styrene 

2.76 

3.19 

3.66 

3.96 

4.70 

5.36 

6.03 

9.61 

10.5 

5.86 

11.1 

5.55 

8.62 

2.50 

0.98 

4,667 

12.4 

6.94 

11.1 

5.55 

8.62 

3.08 

0.98 

,334 

9.03 

5.69 

9.71 

5.24 

7.86 

2.25 

0.83 

4,319 

10.7 

6.74 

9.71 

5.24 

7.86 

2.77 

0.83 

4,936 

11,2 

6.89 

9.97 

5.08 

7.84 

1.68 

<0.1 

5,165 

11.2 

6.89 

9.97 

5.08 

7.84 

2.07 

<0.1 

5,903 

10.24 

6.15 

10.3 

5.29 

8.11 

2.14 

0.637 

4,717 

11.4 

6.86 

10.3 

5.29 

8.11 

2.64 

0.637 

5,391 

Total hydrocarbons 

by species 

ition 

137,115 38,167 144,900 39,697 152,308 42,164 144,774 

Ijierts 

H20, X by volume 

N2, X by volume 

02 , X by volume 

C02, X by volume 

H2, X by volume 

CH«, X by volume' 

TOTAL 

40,008 

N0U 

65.9 

16.5 

0.44 

ND 

15.1 

97.94 

Porapak Q column. 

bSP2100/0. IX Carbowax on 100/120 Supelcoport column. 

cHolecular Sieve and Chromosorb 102 columns. 

Not determined. 

ND 

63.7 

15.7 

0.41 

NO 

15.2 

95.01 

NO 

66.1 

16.3 

0.39 

ND 

15.0 

97.79 

NO 

65.2 

16.2 

0.41 

NO 

15.1 

96.91 
P.9 

During the testing at the styrene finishing column vent (SFCV), the 

volumetric flow rate was very low. The measurement performed indicated 

that the flow was approximately 1 (one) standard cubic foot per 

hour (scfh). The description and discussion of the volumetric flow 

measurement is contained in Section 4.2 and Appendix E. The volume flow 

rate results can only be considered estimates since it is suspected that 

a leak was present in the measurement system and the results presented 

could be low. 

The results of testing at the combined hotwell recovery system are 

presented in Table 2-6. 

The sampling locations are described in Section 3, and the test 

procedures are presented in Section.4. 

2-7 
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