EMB Report No. 78-OCM-12C
December 1979
O
SOCMI - FUGITIVE EMISSIONS
CHLOROMETHANES PRODUCTION
DOW CHEMICAL COMPANY
PLAQUEMINE, LOUISIANA
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Emission Measurement Branch
Research Triangle Park. North Carolina
-------
EMB Report No. 78-OCM-12C
Emission Test Report
SOCMI-Fugitive Emissions
Chloromethanes Production
Dow Chemical Company
Plaquemine, LA
December 1979
-------
Table of Contents
I. Introduction 1
II. Summary of Results 2
III. Process Description 7
IV. Sampling and Analytical Procedures 7
Appendices
A. Field Data Sheets
B. Test Log
C. Project Participants
-------
I. Introduction
Under the Clean Air Act, as amended, the Environmental Protection
Agency is required to develop standards of performance for new stationary
sources. These standards are based on the best.systems of emission reduction
(considering costs) that have been demonstrated. EPA is currently developing
a standard for fugitive emissions from synthetic organic chemical manufacturing
processes, and testing was performed at this facility to gather data for
this study.
Testing was performed at Dow Chemical Company's chlorinated methanes
unit at the Plaquemine, Louisiana facility during September 25-27, 1978.
Emission Standards and Engineering Division, EPA personnel performed the
testing.
The purpose of the field study was to perform a complete individual
component survey with a portable VOC analyzer to measure the local VOC
concentration around the component's potential leak source, and based on
that data, compute the frequency of occurrence of leaks based on different
concentration-limit criteria.
A second purpose was to compare the effectiveness of an area monitoring
system in this unit for indicating the presence of leaks when an overall
component survey is used as a base for comparison. Unit walkthrough surveys
with a portable analyzer were also conducted for comparison of leak detection
effectiveness.
-------
II. Summary Of Results
For ease of component identification, the chlorinated methanes unit was
subdivided into six grids. The pumps in each grid were already numbered by
the company. Temporary identification tags were placed on certain equipment
types (such as control valves) to allow relocation for additional testing.
Individual component surveys, where each potential leak source was tested,
were conducted on a grid-by-grid basis. A repetition of the individual
component surveys was conducted for grid 2 and a portion of grid 5.
The results of the individual component survey are presented in Table
II-l. Summaries are presented for each component type as well as for all
components tested. Of the 788 sources tested, 20 (or 3 percent) had VOC
concentrations at the leak interface of greater than 10,000 ppmv. The
results of the individual component survey repetitions are presented in
Table II-2. This table shows the number of readings that were repeatible
and not repeatible for each VOC concentration range. The one incidence of
a non-repeatible result for VOC >10,000 ppm was due to a change in the
status of the pump between tests. The pump had been shut down and blocked off
between the surveys.
A second type of testing was performed to evaluate the effectiveness of
a "walkthrough" screening procedure. Prior to testing, a traverse path was
prepared so that all individual equipment at ground level would be passed at
about one meter upwind and downwind. The path also included a measurement
of the unit perimeter ambient VOC concentrations. The effectiveness of a
walkthrough survey depends on the ability of the portable analyzer to detect
an increase in the local ambient VOC concentration downwind of a source with
VOC concentration greater than 10,000 ppmv. An analysis of the walkthrough
data will be presented in a separate report.
The third type of testing at the facility was to estimate the
capability of the fixed point monitoring system installed by Dow in
identifying sources with concentration greater than 10,000 ppmv that were
located by the individual component survey. A summary of the fixed point
monitor alarms versus sources with concentrations greater than 10,000 ppmv
("leaks") identified by individual component surveys is presented in Table II-3.
For this analysis each equipment leak identified was located on the grid plot
plan and the nearest fixed monitoring point(s) downwind were identified. The
monitor chart records were then consulted to see if an alarm was noted at that
location. Based on this analysis, the fixed monitor system indicated 4
alarms that could have been caused by upwind leaks, out of a total of 22
identified leak sources. The monitor alarms were based on threshold limit
values for the individual compounds, and this could have contributed to the
low leak detection effectiveness. However, for this report no attempt was
made to further evaluate the chart records to see if the lower VOC increases
were measured at the applicable test sites. It is probable that the
meterological conditions, distance from the leak source, and relative
magnitude of each leak would not always result in a local ambient VOC
concentration that would exceed the threshold limit value alarm settings. In
addition, since some equipment items were not readily accessible for component
testing, it is possible that the fixed monitoring system could indicate alarms
-------
when no leak source has been found in the area using individual component
survey techniques.
The field data sheets are included as Appendix A.
-------
TABLE II-l - Summary: Number of Components versus VOC
Concentration at 0 Centimeters from the
Source; Dow Chemical Company, Plaquemine, LA
VOC
Concentration
ppm as methane
< 200
201 - 1000
1001-10,000
> 10000
^ Total
Equipment Type
Pump Seals
dumber
17
7
16
7
47
% OT
Total
36
15
34
15
Control
Valves
Number
46
2
1
3
52
%
88
4
2
6
Valves
Number
558
18
16
8
600
%
93
3
3
1
Open-Ended
Line
Number
44
2
5
1
52
%
85
4
9
2
Pressure
Relief
Valves
Number
7
0
0
0
7
%
100
0
0
0
Flanges
Number
27
2
0
1
30
%
90
7
0
3
Total
Equipment
Number
699
31
38
20
788
%
89
4
5
3
-------
voc
Concentration
ppm methane
< 200
201 - 1000
1001 - 10000
> 10000
TABLE II-2: Component Survey Results
Reproducebility
Number of Data Points with:
Same Result
135
2
8
5
Different Result
3
5
6
1
-------
Table II-3: Summary of Area Monitor Alarms Associated with
Equipment Leaks for 8/27/78 to 10/23/78
Valves
Leak Location
1-8
2-19
2-30
2-31
2-36
2-37
2-29
2-43
2-44
2-45
3-5
3-12
5-1
5-3
5-4
Pumps
Leak Location
2-3
2-8
2-14
2-21
5-5
5-11
6-3
Alarms
No
Yes
Yes
No
No
No
No
No
No
No
No
Yes
No
No
No
Alarms
No
No
No
Yes
No
No
No
Point No.
20
2,3
2,3
3
2,3
2,3
2,3
2,3
2,3
2,3
14,15
14,15
2,3
2,3
14,15
Point No.
1,2,3,
Component
Ml
M3, M4
Same
Ml
M3, M4
Same
Ml
, ' /
Same
Same
M3
Ml, M3
Ml
Ml, M3
Ml
Ml
Component
M2
Ml
Same
M3
Ml
Same
Ml, M3
Total number of leaks = 22
Total number of leaks w/associated alarms = 4
4 -v 20%
leak detection efficiency = jo =
-------
III. Process Description and Operation
Dow Chemical Company produces chloromethanes at the Plaquemine,
Louisiana, facility through hydrochlorination of methanol and chlori-
nation of methyl chloride. The ratios of co-products is flexible,
depending on the desired end products. The process was operating
normally throughout the test period. Testing of acid service equipment
was aborted when an overhead acid valve leak was detected. This leak
was repaired by company personnel but the test was not rescheduled.
Dow employs a fixed monitoring system for detection of elevated
ambient concentration for personnel safety. A 20 point sequential
system with an FID/GC is used. The alarm levels for the various
chemicals are; 25 ppm methyl chloride, 100 ppm methylene chloride,
5 ppm chloroform, 5 ppm carbon tetrachloride, and 0.5 ppm vinyl chloride
monomer.
IV. Sampling and Analytical Procedures
The instrument used to conduct surveys at this facility was a
Century Systems Corporation OVA-108 organic vapor analyzer. The
instrument was calibrated in EPA laboratories in Durham, North Carolina,
prior to shipment to the test site. Methane in air standards were used.
Unit walkthrough surveys were performed by first identifying a
proposed path so that the unit perimeter would be traversed, and all
pumps and control valves at ground level would be surveyed within a
distance of one meter. The instrument was then carried through the
unit along this path with concentrations and location notations recorded
on a strip chart recorder.
Individual component surveys were performed by traversing at the
surface of the potential leak interface to determine local VOC concentra-
tions. The highest observed concentration was recorded on a field data
sheet.
-------
APPENDIX A
FIELD DATA SHEETS
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APPENDIX 8
Test Log
Dow - Chloromethanes
9/25/78
Grid 1 - OVA
Grid 2 - OVA
9/26/78 Perimeter Walkthrough
1300-1430
1445- ?
? -1630
Grid 1
Grid 2
Grid 3
Grid 4
Grid 5
Grid 6
Grid 3
Grid 4
Grid 5
OVA
9/27/78 Grid 2 Walkthrough
1430
Grid 6 OVA
Grid 2 OVA Repeat
1 Tower in Grid 2
Grid 5 Repeat (load rack)
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APPENDIX C
Project Participants
Winton Kelly EMB/ESED, EPA
K. C. Hustvedt CPB/ESED, EPA
R. C. Weber CPB/ESED, EPA
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