United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 79-OCM-13
August 1979
Air
Benzene - Organic
Chemical Manufacturing
Emission Test Report
Ethyl benzene/Styrene
Amoco Chemicals
Company
Texas City, Texas
-------
SOURCE TEST: AMOCO CHEMICALS CORPORATION
ETHYLBENZENE/STYRENE PLANT
TEXAS CITY, TEXAS
by
M. W. HARTMAN
C. W. STACKHOUSE
Contract No. 68-02-2812
Work Assignment 40
EPA Technical Manager: Winton Kelly
Prepared for:
Emission Measurement Branch
Emission Standards and Engineering Division
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
TRW
ENVIRONMENTAL ENGINEERING DIVISION
-------
TABLE OF CONTENTS
1.0 INTRODUCTION 1
2.0 SUMMARY AND DISCUSSION OF RESULTS 3
3.0 PROCESS DESCRIPTION 25
4.0 LOCATION OF SAMPLING POINTS 26
5.0 TEST PROCEDURES 31
APPENDIX A COMPLETE RESULTS & SAMPLE CALCULATIONS
APPENDIX B LABORATORY RESULTS
APPENDIX C FIELD DATA SHEETS
APPENDIX D TEST LOG
APPENDIX E PROJECT PARTICIPANTS
-------
1.0 INTRODUCTION
During the periods of May 7th through llth and May 14th through
18th, 1979, personnel from TRW Environmental Engineering Division,
Energy and Environmental Analysis Incorporated (EEA) and the U. S.
Environmental Protection Agency's (EPA) Emission Measurement Branch
(EMB) conducted tests at Amoco Chemical Company's ethylbenzene/styrene
plant in Texas City, Texas.
This facility was tested in order to obtain and analyze samples to
provide data in support of possible National Emission Standards for
Hazardous Pollutants (Benzene) and New Source Performance Standards
(Organic Chemical Manufacturing Industry).
Samples were taken from the vents to the atmosphere at the hotwell
serving the ethylbenzene recycle column, the polyethylbenzene (PEB)
column, and the styrene purification column, the vent recovery system
serving the benzene/toluene column, and at the inlet and outlet to the
superheater. Liquid samples were taken of the ethylbenzene recycle
column hotwell liquid and of the benzene/toluene column vacuum equipment
condensate.
The emissions analyzed were low molecular weight hydrocarbons as
C, - Cg species, benzene, toluene, ethylbenzene and styrene. In addi-
tion, tests were performed for stationary gases, (C02, 02, N2) flow, and
temperature.
The purpose of testing the hotwell vents and the benzene/toluene
column vent recovery system was to determine benzene concentrations and
total flow at these locations. The inlet fuel gas and the outlet flue
gas of the superheater were tested to determine the benzene destruction
efficiency of the combustion device.
All sampling and analysis were conducted at the plant site. The
exceptions to this were the liquid samples which were refrigerated
-------
and transported to the lab in Raleigh, North Carolina for further
analysis. TRW personnel performed the sampling and analysis. Plant
operating data and process descriptions were obtained by personnel
from EEA, Inc., Durham, North Carolina. The entire operations was
supervised and audited by EPA Emission Measurement Branch personnel.
-------
2.0 SUMMARY AND DISCUSSION OF RESULTS
During the testing at the ethylbenzene/styrene facility in Texas
City, samples were taken at separate processes. For clarity and ease of
explanation, the results and methods are presented in the following
separate sections.
t Section 2.1 Benzene/Toluene Column Recovery System
Section 2.2 Column Hot Well Vents and Liquids
(Ethylbenzene Recycle, PEB, Styrene Purification)
Section 2.3 Steam Superheater
The first week of testing involved sampling and analysis of the
column hot well vents and the benzene/toluene column recovery system.
The samples from the inlet and outlet of the steam superheater were
taken during the second week of testing. The entire area was a
restricted process area. The analytical trailer was set up in an
approved area and monitored daily. All sampling apparatus was assembled
at the trailer and transported to the sampling site at the time of
each test. At the conclusion of each test the equipment and the
samples were returned to the trailer.
-------
2.1 BENZENE/TOLUENE COLUMN RECOVERY SYSTEM
(Figure 2.1, points 2 and 3)1
The recovered liquids from the benzene/toluene recovery system were
obtained at point 2. Point 3 was a sample of the non-condensables from
the recovery system to the plant fuel. Both samples were taken simul-
taneously.
The liquid sample at point 2 separated into a hydrocarbon and a
water layer. The samples were shaken to form a single phase and then
injected into the gas chromatograph. Results are shown in Table 2.1.
The volumes of each layer were measured and the percent water layer is
reported in Table 2.1. The liquid flow rate was determined by recording
the time required to accumulate a total volume of five gallons. The
total condensables recovered were directed into the five gallon container
by closing off the normal recovery drain valve and shunting the flow to
the container by opening the sampling valve.
Results of the analysis of point 3 samples are shown in Table 2.2.
Flows at point 3 were obtained from a plant orifice which was connected
to a square root differential pressure meter. The results of these
flows are shown in Table 2.2. The orifice calibration sheet and example
calculations are contained in the Appendices.
2.2 COLUMN HOT WELL VENTS
(Figure 2.1, sample points 6, 7, 8, 9)
This section includes the results of testing at the ethylbenzene
column hotwell liquid (point 6) and vent to the atmosphere (point 7).
Also discussed are results from the vents of the PEB hotwell (point 8)
The sample location numerical designations are not sequential. Poten-
tial test locations in the process were identified prior to a prelim-
inary survey at the facility. During the initial visit, it was
determined that some of the proposed locations either did not exist
or could not be sampled. To maintain continuity for the overall
project record, the original location designations were retained,
therefore, results for test Points 1, 4, 5, and 10 do not exist.
-------
2
and the styrene purification hot well (Point 9) . The four sampling
points were tested simultaneously. The results of the analyses are
contained in Tables 2.3 through 2.6.
Flows were monitored at the hot well vents (Points?, 8, and 9)
before and after testing with a 4-inch vane anemometer, which was
adapted to fit the two and one half inch vent pipe. The four-inch
diameter was used in the calculations for total flow. Calculations and
data are contained in Appendix A. Flows of the liquids were not deter-
mined.
The liquid samples were analyzed at the Raleigh, N.C. Laboratory.
They were thoroughly mixed and injected into the gas chromatograph.
There was no apparent water/hydrocarbon phase separation in these
samples. The main constituent was water with trace amounts of hydro-
carbons present. The results of the liquid samples are listed in Table
2.3.
2.3 STEAM SUPERHEATER (Figure 2.2)
The purpose of this third series of tests was to determine the
destruction efficiency for the incineration of benzene in the process
heater. The fuel input to the boiler (Point 12), and the outlet to
atmosphere of the steam superheater (Point 11) were tested simulta-
neously and the results obtained by on-site analysis. The benzene
concentration found in the first run at the outlet location was much
higher than expected. Blank tests on the sampling system confirmed that
residual organic contamination was present in the apparatus. The
sampling procedures were changed so that glass sampling flasks were used
in place of the EPA Method 110 flexible bag system. An initial run
indicated that the modified procedure had eliminated the contamination.
However, subsequent samples yielded results that were variable and
2
The test plan included measurement of flow and VOC concentration from
the vent to atmosphere of a collector pump for the ethyl benzene recycle
column and styrene purification column hot well overflows. At the time
of testing, it was determined that the pumping rate from the collector
was metered based on a constant level control and operates continuously.
Therefore, there was theoretically no net displacement of air to the
atmosphere during operation. Preliminary flow measurements confirmed
that no flow to atmosphere was occuring, therefore no samples were
collected for VOC and benzene determination.
-------
inconsistent. In an attempt to clarify the results, blanks on the glass
sampling system and the gas chromatograph injection system were run. A
satisfactory blank of the system was not achieved. Appendix A contains
the blank series that was run during testing. Gas chromatograph results
reported in the following tables are uncorrected for blanks. These
results are continued in Tables 2.7 and 2.8. Table 2.9 contains results
of the benzene destruction efficiency and flow data.
The study of the superheater revealed problems in the testing
procedures. (The sequence of problems are presented with the Superheater
Study in Appendix A. The first problem in testing was the contamination
of the Method 110 Sampling Apparatus. The first test run at the Super-
heater outlet revealed a high level of benzene (^ 60 ppm). The source
of this high level was due impart to the memory effect of the sampling
apparatus being previously used for testing the high levels of benzene
at the hotwell vents. A blanking study of the sampling apparatus revealed
the sample bags contained a 20 ppm level of benzene after being purged
with nitrogen; a check of the flowmeters in the system revealed a 20 ppm
benzene level of contamination. The blanking procedure was carried out
on the detection instruments and a nitrogen purging of the sample loop
gave benzene results of no lower than 4 ppm. An alternative to the
sampling procedure was adapted since adequate cleaning of the Method 110
apparatus could not be achieved.
The sampling system was adapted in order to obtain grab samples in
a glass flask. The glass sampling bomb method also encountered difficulties.
The cleaning of the glass bomb with isopropyl alcohol was believed to
interfere with the benzene reading due to similar retention times. The
10 cc syringe used for sample injection from the glass sample bomb was
determined to be too small a volume to adequately flush a GC sample loop
of 2-4 ml total volume. A blank procedure was attempted on the glass
bomb sample method and the result was approximately at 2 ppm of benzene.
Blanking of the sampling loop and gas chromatograph between each test
run yielded results at the 1 ppm level. This consistent background of
benzene was considered to be due in part to the time for an unheated
sample to purge back to zero.
-------
Ambient samples were obtained with an OVA total hydrocarbon analyzer
and the result was benzene levels ranging from 5-10 ppm. The testing of
the superheater was ended and hypotheses on the testing procedures were
derived from subsequent lab studies and information gathered during
testing. Some of the conclusions are:
1. The sampling appratus cannot be adequately cleaned by
simple purging after exposure to high level aromatics (example -
benzene).
2. Glassware exposed to aromatic compounds cannot be cleaned
using purging and solvent rinses alone.
3. An unheated sample loop on the gas chromatograph does not
purge to zero quickly.
4. The syringe used for sample injection was too small to
adequately flush and fill the G.C. sample loops.
With these testing problems in mind the preparation, sampling
and analysis procedure for further testing of this type have been modified
to accomodate these conclusions.
Due to the configuration of the stack and absence of adequate
ports, an outlet volumetric flow rate could not be measured. Since it
is necessary to calculate the benzene removal effeciency on a mass
basis, a combustion calculation using the fuel and flue gas analysis was
performed to calculate a combustion dilution factor for adjusting the
measured inlet and outlet benzene concentrations to the same volume
basis.
A carbon balance based on the combustion calculations yields
significantly different exhaust gas C02 concentrations from those
directly measured. Based on this difference, it is probable that the
fuel gas analyses are inaccurate. Due to the difficulty of achieving
accurate results on the GC system used for C^ - Cg analysis when C,
exceeds 5 volume %, the results for methane are probably low, and since
hydrogen was determined by difference, that result is probably high.
-------
Due to the difficulties encountered with interferences, blanking,
analysis, and combustion calculations the flue gas analysis obtained at
the superheater cannot be used with confidence. These sampling and
analysis problems have been subsequently remedied and tests conducted
after this do not contain data with these problems.
-------
Noncondensables
from Benzene/Toluene
Column Condenser
Noncondensables
to Plant Fuel System
vj Vent Recovery
| System
^Recovered Liquids
FIGURE 2-1 SAMPLE LOCATIONS - B/T COLUMN VENT RECOVERY SYSTEMS
-------
From
Ethyl benzene
Recycle
Column
Š
Water Sanjle
Vent to
Atmosphere
A
^r*,,^.. .-.V-.V.S
totwel1
From
Styrene
Purification
Š
j
1
1
k
r
i
i
i '
i \
Ve
At
/K
/Overflow
'_-,-, ...-_...
Atmosphere
till
io
urn
\
e
n
n
/
t
Vent to
Atmosphere
A
1 ' "'
'Hotwell
System Purification
Column
Water Out
from
PEP Column
Water Out <-
V
Vent to
Atmosphere
Hotwel1
FIGURE 2.2 SAMPLE LOCATIONS - HOTWELL VENTS
10
-------
Other fuel feeds from process
\\2 Separation Vent
-->
Benzene/Toluene Hotwell Vent
Fuel Mix Drum
Natural Gas
FIGURE 2.3: Steam Superheater System
Amoco, EB/S
Texas City, Texas
I!) Flue Gas
to ATM
Steam Superheater
-------
COMPOUND
*
(RUN 2-1)
BENZENE
TOLUENE
ETHYLBENZENE
WATER
COMPOSITE
(RUN 2-2)
BENZENE
TOLUENE
ETHYLBENZENE
WATER
COMPOSITE
(RUN 2-3)
BENZENE
TOLUENE
ETHYLBENZENE
WATER
COMPOSITE
(AVERAGE)
BENZENE
TOLUENE
ETHYLBENZENE
WATER
COMPOSITE
WEIGHT %
(LIQUID)
59.4
26.3
9.8
4.5
50.9
31.4
6.4
11.3
63.5
23.3
10.6
2.6
57.9
27.0
8.9
6.1
VOLUME %
(LIQUID)
59.4
26.7
10.0
3.9
51.3
32.1
6.6
10.0
63.4
23.6
10.7
2.3
58.0
27.5
9.1
5.4
WEIGHT
(GRAM/L)
522.1
231.2
86.7
39.0
450.9
278.0
57.2
100.0
557.3
204.4
92.8
23.0
510.1
237.9
78.9
54.0
FLOW
(LPM)
1.04
1.10
1.08
1.07
"Liquid sample analysis converted from vapor phase results to equivlent
liquid phase concentration (see sample calculation in Appendix A.)
All values calculated from ppm as benzene.
Runs 2-4 and 2-5 were not included due to process inconsistency.
TABLE 2.1: COMPOSITION OF THE RECOVERED LIQUID STREAM AT THE BENZENE/
TOLUENE COLUMN VENT: SAMPLE POINT 2
12
-------
RUN NO.
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
Flow rate, scfm*, dry
Total (%)
3-1
ppmv as
benzene
1004.3
3993.1
1365.1
45325.4
.4425,5
N.D.
19325.7
337.0
634.9
135.1
77310.5
ppmv as
species
4268.4
9064.2
2129.5
59376.3
4514.0
N.D.
19325.7
273.8
436.5
82.3
99907.5
n/m
64.1
3.9
12.6
76.46
90.4
3-2
ppmv as
benzene
970.7
3861.1
1266.0
40132.0
4145.2
N.D.
17098.0
232.3
359.0
69.1
68133.4
ppmv as
species
4125.4
8764.1
1975.0
52572.9
4228.1
N.D.
17098.0
188.7
246.8
113.4
89312.9
n/m
64.6
3.0
13.0
72.86
89.5
3-3
ppmv as
benzene
947.2
2340.3
1305.7
38605.8
3277.1
N.D.
16361.8
263.6
713.2
170.3
63985.0
ppmv as
species
4025.7
5312.5
2036.8
50573.6
3342.6
N.D.
16361.8
214.1
490.3
103.8
82461.2
n/m
65.7
4.1
12.9
71.74
90.9
N.D. - NOT DETECTED
* @ 200C, latm
n/m - not measured
TABLE 2.2 POINT 3 ANALYSIS SUMMARY
B/T COLUMN VENT
13
-------
Run #
Benzene*
Ethyl benzene
Styrene
6-1
N.D.
N.D.
N.D.
6-2
443
5
N.D.
6-3
611
29
11
*A11 values given in ppm as benzene (volume/volume)
N.D. - NOT DETECTED
TABLE 2.3: COMPOSITION OF THE ETHYLBENZENE RECYCLE
COLUMN HOT WELL WATER
(POINT 6)
14
-------
RUN NO.
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
Flow rate, acfm.
Total (%)
7-1
ppmv as
benzene
0.55
N.D
N.D
11.7
N.D.
N.D.
4843.4
5778.8
6661
186
17481.4
ppmv as
species
2.3
N.D.
N.D.
15.3
N.D.
N.D.
4843.4
4695.4
4579.4
113.3
14249.1
6.5
72.6
18.0
<30 Dpm
9.78
98.5
7-2
ppmv as
benzene
2.5
N.D.
N.D.
35.3
N.D.
N.D.
4667.6
5452.6
6446.7
180.5
16785.2
ppmv as
species
10.5
N.D.
N.D.
46.2
N.D.
N.D.
4667.6
4430.2
4432.1
no
13696.6
5.5
73.6
18.0
<30 DPm
8.36
98.4
7-3
ppmv as
benzene
2.7
3.7
N.D.
15.4
N.D.
N.D.
4176.1
3881.1
3164.6
79.7
11323.3
ppmv as
species
11.7
8.4
N.D.
20.2
N.D.
N.D.
4176.1
4776.8
4603.1
130.8
13727.1
4.7
71.6
17.6
<30 ppm
8.29
95.2
N.D. - Not Detected
TABLE 2.4 - POINT 7 ANALYSIS SUMMARY
PEB COLUMN VENT
15
-------
RUN NO.
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
Flow rate, acfm.
Total (%)
8-1
ppmv as
benzene
948.2
57.2
22.2
8.7
3.22
N.D.
325.0
33.2
199.0
19.7
1614
531
ppmv as
species
4029.8
128.2
31.8
11.4
N.D.
N.D.
325.0
27.0
137.4
12.0
4702.6
6.5
74.6
17.2
N.D.
35.35
98.7
8-2
ppmv as
benzene
0.53
4.9
1.2
42.0
N.D.
N.D.
1460.4
34.1
215.3
22.9
1781.3
1798
ppmv as
species
2.3
11.1
1.9
55.0
N.D.
N.D.
1460.4
27.7
148
13.9
1720.3
5.5
80.6
10.3
N.D.
38.35
96.6
8-3
ppmv as
benzene
0.91
5.9
N.D.
37.7
N.D:
N.D.
1120.5
40.7
986.7
102.7
2285.9
ppmv as
species
3.9
13.5
N.D.
37.4
N.D.
N.D.
1120.5
33.0
678.4
62.6
1966.3
4.7
77.5
11.2
N.D.
8.61
93.6
N.D. - Not Detected
TABLE 2.5 - POINT 8 ANALYSIS SUMMARY - ETHYLBENZENE COLUMN VENT
16
-------
RUN NO. 9
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
NŁ> % by vol.
02, % by vol.
C02, % by vol.
Flow rate, acfm.
Total (%)
9-1
ppmv as
benzene
31.2
4.8
4.4
11.3
N.D.
N.D.
36.3
346.3
9726.4
1281.7
11442.4
24339
ppmv as
species
132.5
11.0
6.9
14.9
N.D,
N.D.
36.3
281.4
6686.9
781.0
7950.9
6.5
75.6
15.4
<30 ppm
8.41
98.3
9-2
ppmv as
benzene
6.0
1.1
N.D.
7.7
N.D.
N.D.
36.9
361.8
10364.4
1639.7
12417.6
23035
ppmv as
species
25.4
2.4
'N.D.
10.0
N.D.
N.D.
36.9
293.9
7125.5
999.3
8493.4
5.5
73.6
16.3
<30 ppm
8.23
96.3
9-3
ppmv as
benzene
2.8
1.0
1.3
9.0
5.6
N.D.
73.8
332.4
6383.2
749.6
7558.7
ppmv as
species
12.2
2.4
2.2
11.9
5.7
N.D.
73.8
270. C
4388.6
456.8
5223.7
4.7
73.6
15.4
<30 ppm
3.49
94.2
N.D. - Not Detected
TABLE 2.6 - POINT 9 ANALYSIS SUMMARY - STYRENE PURIFICATION
HOTWELL PUMP VENT .
17
-------
RUN NO. 11
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
Flow rate, scfm*, dry
Total (%)
11-1
ppmv as
benzene
0.12
N.D.
N.D.
4.2
N.D.
0.72
2.8
1.6
8.6
2.0
20.0
ppmv as
species
0.5
N.D.
N.D.
5.5
N.D.
0.86
2.8
1.3
5.9
1.2
18.1
4.7
76.7
8.6
6.6
--
96.6
11-2
ppmv as
benzene
1.2
4.6
51.0
96.5
N.D.
3213.7
34.0
12.2
51.5
5.0
3469.7
ppmv as
species
4.9
10.4
79.6
126.5
N.D.
3213.7
34.0
9.9
35.3
3.1
3517.4
4.1
74.2
8.6
13.1
100.0
11-3
ppmv as
benzene
0.23
N.D.
N.D.
N.D.
N.D.
N.D.
11.9
4.6
27.8
5.5
50.0
ppmv as
species
0.97
N.D.
N.D.
N.D.
N.D.
N.D.
11.9
3.5
18.2
3.1
37.67
3.7
75.5
8.6
12.2
100.0
N.D. - Not Detected
* 8 200C, latm
TABLE 2.7 - POINT 11 ANALYSIS SUMMARY - STEAM SUPERHEATER OUTLET
18
-------
RUN NO. 11
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol .
02, % by vol.
C02, % by vol.
Flow rate, scfm*, dry
Total (%)
11-4
ppmv as
benzene
0.21
N.D.
N.D.
55
N.D.
N.D.
5.5
3.1
22.6
4.6
91.0
ppmv as
species
0.9
N.D.
N.D.
72.1
N.D.
N.D.
5.5
2.5
15.5
2.8
99.3
5.7
73.8
8.6
11.9
100.0
11-5
ppmv as
benzene
5.0
N.D.
N.D.
N.D.
6.6
N.D.
4.4
1.5
8.5
0.9
26.9
ppmv as
species
21.1
N.D.
'N.D.
N.D.
6.9
N.D.
4.4
1.2
5.8
0.5'
39.9
4.6
79.8
8.8
6.8
100.0
11-6
ppmv as
benzene
6.3
3.8
4.2
5.0
204.4
0.5
15.3
1.7
8.6
0.9
250.7
ppmv as
species
26.8
8.6
6.5
6.6
208.5
0.42
15.3
1.4
5.9
0.55
280.57
3.85
81.3
7.7
7.2
100.1
N.D. - Not Detected
* 0 20°C, latm
TABLE 2.7 - POINT 11 ANALYSIS SUMMARY (CONTINUED)
STEAM SUPERHEATER OUTLET
19
-------
RUN NO. 11
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
Flow rate, scfm*, dry
Total (%)
11-7
ppmv as
benzene
1.5
N.D.
N.D.
N.D.
56.2
N.D.
4.5
1.7
10.6 ,
1.2
75.7
ppmv as
species
6.4
N.D.
N.D.
N.D.
57.3
N.D.
4.5
1.4
7.3
0.73
77.6
2.9
82.2
7.9
7.0
100.0
AVERAGE
ppmv as
benzene
2.1
4.2
27.6
40.2
89.1
1071.6
11.2
3.8
19.7
2.9
1272.4
ppmv as
species
8.8
9.5
43.1
52.7
90.9
1071.7
11.2
3.0
13.4
1.7
1306.0
4.2
77.6
8.4
9.3
99.5
ppmv as
benzene
ppmv as
species
i
N.D. - Not Detected
* & 200C, latm
TADLE 2.7 - POINT 11 ANALYSIS CUMCAIY (CONTINUED)
STEAM SUPERHEATER OUTLET
20
-------
RUN NO. 12
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
HŁ % by vol.**
Total (%)
i;
ppmv as
benzene
Not Run
ii
H
n
n
n
1165.3
434.3
2770.5
494.4
4864.5
0
3
1
8
86
100
M
ppmv as
species
1165.3
352.9
1904.7
301.3
3724.2
.6
.3
.6
.5
.0
12
ppmv as
benzene
13389.8
699.0
332.9
N.D.
N.D.
930.2
1188.6
310.2
2014.5
392.8
19258.0
0
2.
1
13
82
100.
'-2
ppmv as
species
56906.8
1586.8
519.4
N.D.
N.D.
781.4
1188.6
252.1
1385.0
239.4
62859.5
8
2
8
2
0
12
ppmv as
benzene
18888.5
425.0
502.1
N.D.
N.D.
N.D.
1183.2
594.5
1143.5
N.D.
22736.8
0
5.E
1.?
8.1
83.?
100. (
-3
ppmv as
species
80276
964.8
783.3
N.D.
N.D.
N.D.
1183.2
483. C
786.1
N.D.
84476.4
)
i
)
)
N.D. - Not Detected
**
by difference
TABLE 2.8 - POINT 12 ANALYSIS SUMMARY - STEAM SUPERHEATER INLET
21
-------
RUN NO. 12
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons jJy:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
H2 % by vol.**
Total (%)
12-4
ppmv as
benzene
26701.9
14862.0
12331.3
N.D.
N.D.
972.1
1098.6 .
354.8
2102.2
385.2
58808.1
ppmv as
species
113483.1
33736.7
19236.8
N.D.
N.D.
816.6
1098.6
288.3
1444.6
234.7
170339.4
0
5.8
2.6
8.5
83.1
100.0
12-5
ppmv as
benzene
14904.1
770.8
237.7
41.4
273.2
N.D.
989.0
378.4
989.4
177.7
.18761.7
ppmv as
species
63342.5
1749.7
370.9
54.3
278.6
N.D.
989.0
307.4
680.2
108.3
67880.9
4.8
<.l
7.3
87.8
100.0
12-6
ppmv as
benzene
15317.4
693.9
143.4
25.3
1425.0
N.D.
1110
450
905
155
20225
ppmv as
species
65098.9
1575.1
223.8
33.2
1453.5
N.D.
1110
365.6
622.2
94.5
70576.8
0
3.8
<.l
7.2
88.9
100.0
N.D. - Not Detected
** by difference
TABLE 2>g _ pQINT ^ ANALYsiS SUMMARY (CONTINUED)
STEAM SUPERHEATER INLET
22
-------
RUN NO. 12
Species Analysis
C-l
C-2
C-3
C-4
C-5
C-6
BENZENE
TOLUENE
ETHYLBENZENE
STYRENE
Total Hydrocarbons By:
species summation
total HC analyzer
Inerts and Flow Data
H20, % by vol.
N2, % by vol.
02, % by vol.
C02, % by vol.
H2 % by vol. **
Total (%)
12-7
ppmv as
benzene
15087.6
708.6
208.9
32.2
758.0
N.D.
1524.6
710.0
1482.6
207.9
20720.4
ppmv as
species
64122.3
1608.5
325.9
42.2
773.7
N.D.
1524.6
576.9
1019.3
126.7
70120.1
0
13.2
1.2
7.1
78.5
100
AVERAGE
ppmv as
benzene
17381.6
3026.6
2292.7
1179.9
466.7
1629.7
302.2
26274.4
ppmv as
species
73871.6
6870.3
3576.7
1179.9
375.2
1120.3
184.2
87178.2
0
5.6
1.2
8.7
84.4
100
ppmv as
benzene
ppmv as
species
N.D. - Not Detected
** by difference
TABLE 2.8 - POINT 12 ANALYSIS SUMMARY (CONTINUED)
STEAM SUPERHEATER INLET
23
-------
RUN NO.
ro
-P.
Stack Outlet
Benzene Cone.
(ppm wet)
Stack Oxygen
Cone. (%v/v wet)
Stack Moisture
(as analyzed in
sample)
Benzene Emission
(ppm @ 3% 02 dry)
Fuel Inlet
Benzene Cone, (ppm)
Dilution Factor
Benzene Removal
Efficiency (%)
2.8
8.6
4.7
4.43
1165.3
4.02
99.0
34.0
8.6
4.7
53.77
1188.6
4.26
87.8
11.9
8.6
4.7
18.82
1183.2
4.11
95.9
5.5
8.6
4.7
6.95
1098.6
5.27
97.4
4.4
8.8
4.7
7.08
989.0
4.04
98.2
15.3
7.7
4.7
22.42
1110.0
3.68
94.9
4.5
7.9
4.7
6.70
1524.6
3.64
98.9
TABLE 2.9: SUMMARY OF RESULTS - STEAM SUPERHEATER
-------
3.0 PROCESS DESCRIPTION
(to be supplied by EPA)
25
-------
4.0 LOCATION OF SAMPLING POINTS
Sampling locations are described in separate sections for the
following equipment groups:
0 4.1 Benzene/Toluene column recovery system
4.2 Ethyl benzene Recycle, PEB, Styrene Purification
Column's hot well vents and liquids
4.3 Steam Superheater
The sample points are shown schematically in Section 2 and are
shown specifically in Figures 4.1 through 4.3 in this section.
4.1 BENZENE/TOLUENE COLUMN RECOVERY SYSTEM (Figure 4.1)
Point 2 was the recovered liquids from the benzene/toluene column
vacuum equipment condenser. The flow was diverted through the drain
valve to a five gallon container. After the flow measurement was
obtained a sample was taken at this point. The non-condensables from
the final accumulator are directed to the plant fuel mix drum. Sample
point 3 was located at the inlet flange tap at the flow orifice in this
line.
4.2 ETHYLBENZENE RECYCLE, PEB, STYRENE PURIFICATION COLUMN'S HOT WELL
VENTS AND LIQUIDS (Figure 4.2)
Point 6 was a sample taken of the hot well liquid from the Ethyl -
benzene recycle column. Point 7 was taken from the gaseous vent of the
same hot well. Point 8 was taken from an adapted vent at ground level
from the PEB column hot well. The normal vent was blocked off to main-
tain flow through the adapted vent. Point 9 was taken from the vent of
the styrene purification hot well liquid.
26
-------
4.3 STEAM SUPERHEATER (Figure 4.3)
Point 12 was the superheater inlet fuel gas and Point 11 the
exhaust flue gas. The fuel sample was taken directly from the high
pressure fuel stream by installing a regulator valve after a plant drain
valve. The outlet was located 120' above ground level at a point 20'
above the superheater.
27
-------
Figure''4.1 Benzene/Toluene Column Vent (Sampling Location #2 & #3).
BLOCK
VALVE
FROM FINAL
ACCUMULATOR
\/
TO GAS
SAMPLING
SYSTEM
r
TO
PROCESS AND PT. 3
A
FLOW VALVES
BLOCK
VALVE
DRAIN VALVE
3" PIPE
ORIFICE
FROM FINAL
ACCUMULATOR
5 GALLON
SAMPLE
DRUM
D/P CELL
TO FUEL
SYSTEMS
28
-------
VENT
T
i
z
^
1
o
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UJ
Q_
o o
cŁ en
u.
1
i
"^
i
<^^
i
i
1
-
i
i
i
:
'X/
>Ťv
r
Vo
i
FLOW
-^ ' BLOCKED
7 3/4" OC
TO
ANEMOMETER & GAS
SAMPLING
SYSTEM
7h
.L-y
I r
^C
-^"^ ^t
_4 rj
L*iJ
HOTWELL LIQUID
ADAPTED
/ TO 7 3/4" OC
TO ANEMOMETER &
GAS SAMPLING
>.
T]
LJ
Ť
SYSTEM
0 ~j
z
s:
\
__>
_i
o
0 7 3/4" 0_C^
UJ
1
0
^^
<^~
o
UJ
a;
UJ
z
/N
4=^
.>^\
ui VJ
J
i
I
i
i
M
z
a 20
IE r^
i
- x/
21. .. v
o
IX.
u.
^
\
h ,J
*Ł ^ i
ť - ' ť-
-1
i
i
*
HOTWELL LIQUID
ZL
s:
ra
i
i 1
o
c_>
z
CD
ef
CJ
i i
U.
1 (
o:
^^
_J
Q.
UJ
Z.
UJ
a:
>-
h-
oo
s:
o
CŁ
U.
\y
Nr
Pi
r
i
!
f
i
LT)
i^
i
f
nL
v^
VENT
j
:
;^_.7 3/4" 0(
.
W>
i
^^
HOTWELL LIQUID
Figure 4.2: Ethylbenzene Recycle, PEB, Styrene Purification Columns (Sampling Locations 6, 7, 8, & 9).
-------
Figure 4.3: Boiler Flue Gas Stream (Sampling Locations #11 & #12).
-10'
CO
o
ro
O
SAMPLE PORT
120'
, SAMPLE
-CAN 1
FUEL INLETS ''
FROM FUEL -
MIX DRUM
GROU
TO
BURNERS
12"
BLOCK VALVE
ADAPTED OR ADAPTOR.
1/4" TUBING
FINE ADJUSTMENT
VALVE
d
II
U-sFLOW
r METER
\/
TO SAMPLING
SYSTEM
30
-------
5.0 SAMPLING & ANALYSIS PROCEDURES
5.1 SAMPLING PROCEDURES
Figure 5.1 diagrams the sampling apparatus used during testing at
Texas City. This system was chosen due to the restricted process and
safety requirements of the plant. The collection system consists of a can
which seals at a vaccum of 15" mercury (Hg), a bag evacuated to 29" Hg,
a flowmeter for metering gas, and teflon tubing and connections which
serve as a sample line.
The procedure used was to evacuate the can using the outside self-
sealing valve. After a vacuum was achieved, the can vacuum was checked
by placing a vacuum gauge on the outside valve and monitoring the
vacuum. If the pressure did not drop more than 1" Hg, the can was
considered leak-free. The second step was to evacuate the bag to 29"
Hg. The same leak check was then made on the bag. The flowmeter and
can were next transported to the site where the sample was to be taken.
The flowmeter was plugged in and turned on at the appropriate time and
the sample extracted from the stack.
For sampling Points 3 and 12, the teflon line was connected
directly to the stack and purged. It was then plugged into an evacuated
bag and the pressure of the stack filled the bag over a period of time.
For sampling Points 7, 8, and 9, the teflon tube was inserted into the
vent pipe and the evacuated can drew the sample into the can over a
period of time.
For run 11-1, the evacuated can method (Figure 5.2) was used for
drawing a sample into the bag. When analysis was run on the contents,
it proved to be biased high, due to residual benzene being present in
the flowmeter and sampling line. The system was modified to withdraw a
sample through a precleaned glass bomb. The bomb (which has an inlet
and outlet valve along with a septum point as shown in Figure 5.3)
31
-------
was then transported to the trailer for chromatographic analysis.
Figure 5.4 presents a representative gas sample run. This procedure was
repeated for run 11-2 through 11-7.
5.2 FLOW PROCEDURES
Flows were measured on points 7, 8, and 9 by using a vane anemom-
eter which was adapted to the pipes. The calibration data and flow
measuring diagram is contained in Appendix A. Point 8 flow and sampling
was done through an adapted pipe so that it could be accessible. The
normal vent, which was 70' above ground level, was blocked off during
flow measurement and sampling.
At point 2, the valves were controlled during sampling in order to
redirect the condensate to a five gallon container. The flow was obtained
by measuring the time it took to fill the container. A plant orifice
was used to measure the gas flow at point 3. The results are shown in
Table 2.2. An example calculation is presented in Appendix A.
The sampling point at points 11 and 12 were inaccessible to flow
measurement. The destruction efficiency was determined using flow
calculations as described in Section 2.
5.3 ANALYTICAL PROCEDURES
Analysis was performed on site on all gaseous samples. The liquid
samples were refrigerated and transported to the laboratory in Raleigh
for liquid gas chromatographic analysis. Three gas chromatographs were
used in the analysis of the samples. The first instrument (Shimadzu
Mini-1) was dual flame ionization detection (FID) equipped with two
poropak Q columns. This gas chromatograph was used to determine the
lower molecular weight hydrocarbons (C^ - Cg). The second GC was also a
dual FID (Shimadzu Mini-1), which contained a 5% OVIOl/Bentone 34 column.
The third was an AID portable thermal conductivity detector GC used for
quantitative detection of stationary gases. The gas samples were trans-
fered to the gas chromatograph through a one millilHer sample loop,
this allowed consistency with the external calibration standards.
Calibration standards of methane (C-|), ethane ^K propane (C,), butane
(C.), pentane (Cg) and hexane (Cg) were used on the Poropak Q column for
low molecular weight hydrocarbons. Only benzene was available as a
32
-------
calibration standard on the OV-101 column. From the benzene numbers
obtained in the calibrations a response factor was applied to obtain the
concentrations of the individual compounds (See Appendix A).
Blanks of the system were performed and a blank series is listed in
Appendix A. This is discussed in Section 2.
The analysis of the fuel gas, by GC/FID, indicated a saturation
effect of the detector occurred when more than 5% total hydrocarbons
were introduced. This saturation effect was remedied by diluting the
fuel gas samples 100:1 before analysis. The dilutions were performed on
a rotameter dilution board and the results were checked by using $2 an<-1 H
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 GG/FID.
33
-------
PROBE
GLASS SAMPLE BOMB
QUICK DISCONNECT
\
f- .-.,
SAMPLING
BAG
1
1
1
i l
1 1
/
FIGURE 5.1 - Basis Sampling Apparatus
34
-------
PROBE
NEEDLE VALVE
FLOWMETER _ _
1 SAMPLING
BAG
1
1
1
1
1
I
1
1
1
1
1
1
1
1
QUICK DISCONNECT
EVACUATED
CAN
Figure 5.2. Evacuated Can Sampling Apparatus
35
-------
SEPTUM CAP
GO
CTl
FIGURE 5.3 GLASS SAMPLING BOMB
------- |