EMB Report 78-OCM-12E
December 1979
CD
AIR POLLUTION
EMISSION TEST
O
u I
PETROLEUM REFINERY
FUGITIVE EMISSIONS
Phillips Petroleum Company
Sweeny Refinery
Sweeny, Texas
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-12E
Emission Test Report
Petroleum Refinery
Fugitive Emissions
Phillips Petroleum Company
Sweeny Refinery
Sweeny, Texas
December 1979
-------
Table of Contents
1. Introduction 1
2. Summary of Results 2
3. Process Description 14
4. Sampling and Analytical Procedures 15
Appendix
A. Field Data Sheets 16
B. Test Log 118
-------
I. Introduction
Under the Clean Air Act, the Environmental Protection Agency is
required to develop emission standards for air emissions which have been found
to cause adverse health effects, and for new stationary sources which may
contribute significantly to air pollution. EPA is currently gathering back-
ground information to develop a National Emission Standard for Hazardous
Pollutants to control benzene emissions, and in addition New Source Performance
Standards are being developed for control of volatile organic emissions from
synthetic organic chemical manufacturing and petroleum refining operations.
Fugitive emissions, such as leaks from equipment seals, can be a significant
source of emissions. Therefore a field testing program is necessary to gather
data for these studies.
Testing was performed at Phillips Petroleum Company's Sweeny Refinery, Sweeny,
Texas during March 5-8, 1979 by Emission Standards and Engineering Division, EPA
and Engineering Science Inc., McLean, Virginia personnel.
Six processing units were surveyed to determine localized volatile organic
compound concentrations around individual pieces of equipment with a portable
analyzer. Measurements were made at the surface of potential leak sources. These
results were used to calculate the frequency of occurrence of various concentration
ranges.
In addition, undirected and directed maintenance activities were performed
by plant personnel on equipment having high concentration measurements during
initial tests. After maintenance, the equipment was retested to determine
VOC concentration after repair. This information was then used to estimate
leak repair effectiveness.
-------
II. Summary of Results
The results of individual equipment surveys are presented in Tables II-l
through II-7. The data are presented for different equipment types as well as
for total equipment. Also, separate summaries have been prepared for each
different unit tested. The field data sheets from which these summaries were
prepared are included in Appendix A.
The results of maintenance activities in the ethylene unit are tabulated
in Table II-8. During the initial survey, those valves with source concentration
readings greater than 10,000 ppm were identified. Refinery personnel then
attempted repairs in the absence of the test crew. These undirected repairs
are identified by a yes or no in the "Undirected Maintenance Attempted" column.
The next column in Table II-8 presents the test concentration when the test
team returned, usually one day later. The next columns indicate whether or not
directed maintenance was attempted and the readings after additional repairs.
(Note: In this analysis, "undirected repairs" are those that are performed without
using a monitoring instrument to evaluate the success of repair. "Directed
Maintenance" are those in which an instrument is used during repair to determine
if VOC concentration at the leak have been reduced.)
The effectiveness of on-line repair procedures are summarized in Table II-9.
A total of 52 valves were included in data collection. However, six valves were
either mislabeled or not found by the plant maintenance crew and were deleted from
data analysis. Of the remaining forty-six valves, thirty-seven were subjected
to undirected maintenance. Fifty-nine percent were reparied. Then, of the
remaining fifteen that were not repaired, fourteen were subjected to directed
maintenance. Of these, five (or 36%) were reparied. The combination of
undirected and directed maintenance resulted in a repair rate of 73%. The other
nine valves included in the data were not subjected to undirected maintenance due to
defects observed by inspection, or were found after undirected repairs to adjacent
equipment. Of the total forty-six valves tested, repairs were completed for
twenty-nine, or 63%. 2
-------
TABLE II-U
Summary of Results -
Total of ALL Units T
Sweeny, Texas
[C Concentration versus Occurrence Frequency
" d; Phillips Petroleum Co., Sweeny Refinery,
VOC Concentration
ppn as hsxane
0-200 '
201 - 1000
1001 - 10000
> 10000
TOTAL
jj
*at OCM from t
Equipment Type '
Pump
Seals
7."
124
14
11
41
190
le sour
%
65
7
6
22
:e
Compressor
Seals
# ;
25
4
3
1
33
>%
76
12!
9
3
Control
Valves
7f
50-
2
3
13
68
%
i
74
3
4
19
Other
Valves
, i
.JLJ JL'
i
2126
143
73
222
2564:
V
83 .'
6
3
9,
Open-E
Lin
>
j, t
337
23
21
39
420
nded
es*
%
.
80
5
5
9
Drains
ซ**ซ**ซซ ซ^ซtซMmi.BtCT-mTO^ ป
-* j #
2782
198
120
325
3425
* !
'81
6
4
9
-------
TABLE II-2: Summary of Results - VOC Concentration versus Occurrence Frequency
Unit 9 (Crude Unit); Phillips Petroleum Co., Sweeny Refinery,
Sweeny, Texas
VCC Concentration
ppn as hexane
0-200
201-1000
1001-10000
> 10000
Total
*at OCM from
Equipment Type
Pun-
Sea
21
2
2
4
29
he sour
IP
Is
72
7
7
14
ce
Compressor
Seals
#
t
%
Con
Val
10
0
0
1
11
trol
ves
%
91
0
0
. 9
Other
Valves
# ' j *'
325
2
1
2
330
'"V.
98
.6
.3
.6 i
Open-Ended
Lines*
49
1
2
1
53
-
. %
92
2 '
4
2
Drai
]
18
2
0
0
20
ns
%
90.
10
0
0
t
Other
!
x
All
Equipment
. #
423
7
5
8
443
4
.95
2
1
2
-
-------
TABLE II-3:
Summary of Results - VOC Concentration versus Occurrence Frequency
Unit 4 (FCC Gas Plant); Phillips Petroleum Co., Sweeny Refinery,
Sweeny, Texas
VOr Pnnrpnt ration
ppra as hexane
0-200
201-1000
1001-10000
>10000
w Total
*at OCM f rom tl
Equipment Type
Pump
Seals
ซ
22
3
0
1
26
e soun
%
.Tl 1
84
12
0
4
e
Compressor
Seals
#
%
Control
Valves
*
6
0
0
0
6
%
100
0
0
0
Other
Valves
*" ". *
184
3
2
17
206
! *
*-'
Open-Ended
Lines *
#
.ป ซ,_ Y - ซป -.
89"
1
1
8 i
39
0
0
0
39
Drains
f l
100
0
0
0
20
0
0
0
20
%
** *-'A. - - *
1 '
100.
0
0
0
Other
# i
.
All
Equipment
% 1 #
271
6
2
18
297
% :
91
2
1
6
-------
TABLE II-4: Summary of Results - VOC Concentration versus Occurrence Frequency
Unit IOB (Natural Gas Liquids Plant); Phillips Petroleum Company,
Sweeny Refinery, Sweeny, Texas
VOf Tonrpnt ration
ppm as hexane
0-200
201-1000
1001-10000
> 10000
Total
*at OCM from
Equipment Type
Pump
Seals
*
10
1
1
2
14
he sour
%
71
7
7
14
ce
Compressor
Seals
#
.
%
Control
Valves
#
%
Other
Valves
# *'.
f . -^
114
3
2
3 '
122
\.f
93
2.5
2
2.5
.
Open-Ended
Lines*
#
26
1
1
8
36
. ' /O
72
3
3
22
Drains
# j
6
0
0
0
6
%
100
0
0
0
Other
f. i
.
*
All
Equipment
- #
156
5
4
13
178
* i
88
3
2
7
-
-------
TABLE II-5: Summary of Results - VOC Concentration versus Occurrence Frequency
Unit 12 (Ethylene); Phillips Petroleum Co., Sweeny Refinery,
Sweeny, Texas
VOC Concentration*
ppm as hexane
0-200
201-1000
1001-10000
> 10000
Total
*at OCM from
Equipment Type
PUIT
Sea
^igrtJ^i.i.' *.
#
35
3
4
21
63
;he sou
IP
Is
%
56
5
6
33
%ce
Compressor
Seals
#
10
3
3
1
17
%
59
18
18
6
Control
Valves
#
12
0
2
11
25
*
%
48
0
8
.44
Other
Valves
4
# '
665
48
28
121
862
*'
^n.,...
1
77 ;
6
3
14
Open-Ended
Lines*
#
69
7
2
12
i
90
%
77
8
2
13
Drai
M ****ซ**ป;
# :
30
5
0
4
39
ns
%
77
13
0
10
Oth
'y*"ปi Mn%.>ปii-.<
#. !
;
er
%
All
Equipment
#
821
66
39
170
1096
%
.75
6
4
15
-------
TABLE II-6: Summary of Results - VOC Concentration versus Occurrence Frequency
Unit 11 (Reformer); Phillips Petroleum Co., Sweeny Refinery,
Sweeny, Texas
VOC Concentration
ppm as hexane
0-200
201-1000
1001-10000
> 10000
ฐ=>- Total
*at OCM fr
Equipment Type
Pun
^ Sea
10
0
2
3
15
im the
IP
Is
67
0
13
20
;ource
Compressor
Seals
# :
15
1
0
0
16
%
9.4
6
0
0
Con
Val
22
2
1
1
26
*
trol
ves
%
85
8
4
4
Other
Valves
t U "" '
I '(
546
54
21
49
670
<,
81
8
3
7
Open-Ended
Lines *
#
73
7
7
6
93
i
79
8
8
6
Drains
17
3
5
2 '
27
63 .
11
19
7
Oth
#.
er
~~~ "i
*
All
Equipment
#.
683
67
36
61
847
i
.81
8
4
7
-
-------
Table II-7: Summary of Results - VOC Concentration versus Occurrence Frequency
Unit 15 (Hexane Isomerization): Phillips Petroleum Co., Sweeny Refinery,
Sweeny, Texas
VOC Concentration
porn as hexane
0-200
201-1000
1001-10000
> 10000
Total
*at OCM fro
Equipment Type
Pump
Seals
#
26
5
2
10
43
n the s
%
60
12
5
23
>urce
Compressor
Seals
*
%
Control
Valves
#
%
.
Other
Valves
A
\
292
33
19
30
374
-
*'
1
78. ;
9
5
8
Open-Ended
Lines*
#
81
7
9
12
109
%
74
6
8
11
Drai
# !
29 :
2
4
3
38
.
ns
.<
76 .
5
11
8
!
Oth
41
TT
:
er
i
i
Al
Equip
#
428
47
34
55
564
1
ment
76
8
6
10
-------
TABLE 11-8: 'Block Valve Repair Data^^iillips Petroleum Co., Sweeny,'Texas'
Tag
Number
32a
32b
32c
32d
28
16
10
7
4
367
*366
364
362
360
359
Untagged
358
361
Untagged
*356
354
352
65
64
64a
315
Date
Screened
3/6/79
ii
n
n
it
n
n
n
n
3/5/79
n
n
it
it
n
.
n
n
_
n
n
n
3/6/79
n
ป.
n
Initial
Reading3
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
>10000
_
>10000
> 10000
_
NC
> 10000
> 10000
> 10000
> 10000
> 10000
Undirected
Maintenance
Attempted
\
No *
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
No
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
..
Yes
Date
Retested
3/7/79
n
ti
n
ti
n
M
M
n
n
n
n
n
n
ti
n
n
n
n
n
n
n
n
n
M
Retest
Reading
>10000
>10000
>10000
2000
2000
> 10000
100
>10000
200
500
h
NCD
>10000
2000
4000
>10000
NC. .
> 10000
>10000
NC
900
NC
3000
1000
> 10000
3000
Directed
Maintenance
Attempted
\. i
Yes
Yes
Yes
Yes
No
Yes
No
Yes
No
No
No
Yes
No
No
Yes
No
Yes
Yes
No
No
No
No
No
Yes
No
Directed
Maintenance
Readinas .
1
1100
>10000
> 10000
100
> 10000
> 10000
>10000
> 10000
>10000
> 10000
>10000
2
>10000
>10000
>10000
>10000
7000
3
00
Comments
Leaks not tagged dur-
ing initial test
Packing nut tightened
to limit
Packing nut tightened
to limit
Repaired when valve
was backseated
Packing gland bolts
all the way down
Bolts need replacing
Corrosion pi eventing
good gland seating
Needs new packing,
tightened to limit
Leak reduced but needs
new packing
Needs new packing
Mistagged valve, was
not leaking before
maintenance
Valve stem
Gland seat on valve 64
Not found during
initial test
-------
TABLE 11-8 (Continued!
Tag
Number
*311
316
313
312
314
305
*304
*307
306
309
308
310
*302
303
301
317
318
319
320
323
321
322
324
325
*326
327
Date
Screened
3/6/79
n
ii
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
ti
n
Initial
Reading
1000
> 10000
> 10000
> 10000
"> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
> 10000
>10000
>10000
>10000
> 10000
> 10000
> 10000
> 10000
> 10000
Undirected
Maintenance
Attempted
*
Yes
Yes
Yes
Yes
No
Yes
No
No
Yes
No
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Date
Retested
3/7/79
n
n
n
n
n
-
-
3/7/79
_
3/7/79
n
-
n
n
n
n
n
n
n
n
n
ii
n
n
Retest
Reading
NC
> 10000
>10000
> 10000
>10000
5000
NC
>1dooo
1000
1000
>10000
> 10000
>10000
>10000
> 10000
7000
>10000
7000
200
1000
>10000
v
Directed
Maintenance
Attempted
No
Yes
Yes
Yes
No
No
No
Yes
No
No
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
Directed
Maintenance
Readino<;
1
2000
> 10000
> 10000
> 10000
>10000
>10000
>10000
>10000
4000
2
5000
3
Comments
Valve was not >10000.
Open ended line still
> 10000
Needs new packing
Packing all the way
down, no more adjust-
ment
Needs new bolts
^
Sad bolt-cannot tighter
.iquid methane lines-
values have teflon
jacking that requires
leating for good seat-
ing
-------
Table II-9: Maintenance Effectiveness, Block Valves
Phillips Petroleum Company, Sweeny Refinery
1. Total number of valves with VOC >1000ppm
from unit survey 121
2. Total number of valves tested for
maintenance effectiveness 46
% Tested
38%
UNDIRECTED MAINTENANCE
3. Total number subjected to repair attempts 37
4. Successful repairs (VOC <10000ppm) 22
% Repaired
Followup
DIRECTED MAINTENANCE
5. Number of valves unrepaired by undirected 14
maintenance subjected to directed
maintenance
6. Number repaired by followup directed 5
maintenance
% of unsuccessful
repaired by directed
maintenance
7. Total number repaired based on 27
undirected maintenance
subset (3) above
% reparied
59%
36%
73%
8. Total number of repairs including
leaks not found before initial
maintenance
Total % repaired
Total % not reparied
29
63%
37%
12
-------
The repair effectiveness data represent the short-term ability to correct
a leak when found, and do not represent the long term effectiveness of repair.
In addition, since the unit selected for these tests is an ethylene unit which
processes refrigerated low molecular weight materials (liquids at process conditions
but gases at standard conditions), it is expected that the data represent worst-case
conditions. It is possible that the frequency of occurrence of leaks would be
smaller, and that the success of maintenance would be greater for higher molecular
weight compounds that are liquids at standard conditions.
13
-------
III. Process Description
The Phillips Sweeny Refinery is an integrated petroleum refinery and
petrochemical complex. The units surveyed were:
Unit 4 FCC Gas Plant
Unit 9 Crude Unit
Unit 10B Natural Gas Liquids Plant
Unit 11 Reformer
Unit 12 Ethylene Plant
Unit 15 Hexane Isomerization
In addition, surveys were conducted around the wastewater separator and
the benzene storage and truck loading area.
All units were operating normally during the test period.
14
-------
IV. Sampling and Analytical Proecdures
The instrument used to conduct surveys at this facility was a Century
Systems Corporation OVA-108 organic vapor analyzer. The instrument was
calibrated daily at the test site. Methane in air standards were used. Based
on vendor's literature information the response of the instrument to methane
is the same as that for hexane, therefore no adjustments to the instrument meter
readout were made to correct for the use of methane as the calibration standard.
The refinery fenceline surveys were conducted by placing the instrument
probe outside an automobile window and driving around the refinery perimeter
at speeds of 10-15 mph. Measured total hydrocarbon concentrations and their
location were recorded on a refinery plot plan.
Individual component surveys were performed by traversing at the surface
of the potential leak interface to determine local VOC concentrations. The
highest observed concentration was recorded on a field data sheet.
15
-------
APPENDIX A
FIELD DATA SHEETS
16
-------
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Appendix B
Test Log
3/5/79 Fenceline Survey
Unit 12 (ethylene) OVA individual
component testing
3/6/79 Unit 12 OVA individual component
tests, maintenance effectiveness
tests
3/7/79 Unit 4 (FCC Gas Plant) OVA
Unit 11 (reformer) OVA
Unit 15 (hexane isomerization) OVA
Maintenance effectiveness tests
3/8/79 Fenceline survey
Wastewater Separator OVA
Benzene transfer, tanks and loading stations OVA
Unit 9 (crude) OVA
Unit 10B (NGL) OVA
118
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