C.HB
NO. /O-UUVI-
October 1980
CD
O
EMISSION TEST REPORT
BENZENE
FUGITIVE EMISSIONS
PETROLEUM REFINERIES
Sun Petroleum Products Company
Toledo, Ohio
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-12B
EMISSION TEST REPORT
BENZENE
Fugitive Emissions - Petroleum Refineries
Sun Petroleum Products Company
Toledo, Ohio
October 1980
-------
TABLE OF CONTENTS
I. INTRODUCTION 1
II. SUMMARY OF RESULTS 2
III. PROCESS DESCRIPTION 9
IV. SAMPLING AND ANALYTICAL PROCEDURES 10
Appendix
A - Laboratory Report
B - Field Data Sheets
C - Test Log
D - ARCAS Vendor Information for the Fixed Monitoring System
-------
I. INTRODUCTION
Under the Clean Air Act, as amended, the Environmental Protection Agency
is required to develop national emission standards for those air pollutants
which have been found to cause adverse health effects. Benzene has been
listed by EPA as a hazardous air pollutant, and therefore EPA, is currently
developing an emission standard for tenzene emissions for fugitive emissions,
such as leaks from pump seals, valve seals, drains, etc.., for all processes
which produce benzene as a finished product, use Benzene in the production
of other organic chemicals, or produce benz.ene or benzene-containing streams
in the manufacture of organic chemicals.. Testing was conducted at this
facility to develop data for this study.
Testing was performed at Sun Oil Company Ks Toledo Refinery, Toledo,
Ohio, during November 13-17, 1278, by Emission Standards and Engineering
Division, EPA and Engineering Science, Inc. personnel..
Individual component surveys were conducted using a portable. VOC
analyzer. Local VOC concentrations were measured and recorded at the
surface of each potential leak interface. Comparative tests using the
same type portable analyzer were conducted by Sun Oil Company personnel and
the results were recorded on the EPA test data sheets. The results of these
tests were used to compute the frequency of leak occurrence based on
different concentration-limit criteria^
Also, data were collected so that the component survey results could be
used as a basis for comparing the leak-identification effectiveness of unit
area walkthroughs and an area monitoring system installed in one unit at
this facility.
Finally, grab samples of emissions from detected leak sources along with
the liquid handled by that source were collected for chromatographic analysis.
1
-------
The major purpose for this analysis was to determine the relative benzene
proportions in vapor versus liquids at leak" sources.
II. SUMMARY OF RESULTS
The individual component surveys were performed by an EPA test crew
followed immediately by a Sun Oil Company test crew. The results of the
surveys are summarized in Tables II-l to I1-3. Data are presented for
each unit surveyed as well as for the total equipment tested at the refinery.
The EPA and Sun results are presented separately for comparative purposes.
For an additional test procedure comparison, the data were analyzed
to determine for specified concentration ranges the reproducib'ility of
results. This analysis is summarized in Table I1-4. It can be observed
that in 6 of 43 cases Cor 14 percent of readings), the results were
different for VOC >100QO ppm. These data points are listed in Table II-4.
There are two possible causes for differences. First, lower results by
team B could have been caused by a small leak in the instrument probe
system. However, since the different data points are distributed throughout
the survey time, and other data points Immediately before and after do not
show comparable differences, a leak is not probable. The most probable
cause is that the indicated emissions were either variable or very localized
(indicative of small leaks}., and minor variations in timing or probe placement
can cause a different concentration result.
The results of chromatographic analyses of vapor and liquid samples
are presented In detail in Appendix A. The results for benzene distribution
in vapor leak versus liquid source in weight percent are summarized in
Table 11-5. The weight percent benzene in vapor samples has been, calculated
on an air-free basis to allow consistent comparisons to the organic liquid
benzene content.
-------
The results of the walkthrough surveys are presented in Appendix B.
These data will be analyzed in a separate report. Data on the unit 9-4
area monitoring system were taken but are not reported here. Calibration
checks taken both at the gas chromotograph and through the monitoring
pick-up points showed that the aromatics were being removed in the sample
lines prior to instrument. This may have been due to the relatively cold
ambient temperatures during the test. However, this lack of reliability in the
test results made it impossible to use these data to evaluate the effectiveness
of area monitors in detecting equipment leaks.
-------
EPA Data
Table II-l: Summary of Results, VOC Concentra'tion versus Occurrence Frequency;
All Units Sun Oil Company, Toledo, Ohio
VOC
Concentration
ppm hexane
0-200
201-1000
1001-10000
> 10000
TOTAL
Pump Seals
Number
39
11
9
4
63
%
62
17
14
6
Corn]
Num
EQUIPMENT TYPE
pressor Seals
aer
0
$
la
Control Valves
Number
73
5
12
7
97
%
75
5
12
7
Other Valves
Number
1025
42
38
37
1142
%'
90
4
3
3
Open-Ended Lines
Number
47
3
8
3
61
7
lo
77
5
13
5
Drains
Number
*
%
All
Equipment
Number %
1184
61
67
51
1363
87
4
5
4
Drains at this facility are enclosed
Sun Oil Data
VOC
Concentration
ppm hexane
0-200
201-1000
1001-10000
> 10000
TOTAL
EQUIPMENT TYPE
Pump Seals
Number
31
13
7
3
54
i
57
24
13
6
Compressor Seals
Number
0
f
1
Control Valves
Number
73
6
9
9
97
%
75
6
9
9
Other Valves
Number
941
39
32
39
1051
%
90
4
3
4
Open-Ended Lines
Number
40
2
6
3
51
%
78
4
12
6
Drains
Number
r-
lo
All
Equipment
Number %
1085
60
54
54
1253
87
5
4
4
-------
Table II-2: Summary of Results, VOC Concentration versus Occurrence Frequency;
Aromatics Recovery Unit; Sun Oil Company, Toledo, Ohio
EPA Data
VOC
Concentration
ppm hexane
0-200
201-1000
1001-10000
> 10000
TOTAL
Pum
Num
EQUIPMENT TYPE
p Seals
ber
24**
5
3
1
33
%
73
15
9
3
Compressor Seals
Number
0
%
Control Valves
Number
43
4
4
2
53
%
81
8
8
4
Other Valves
Number
687
n
9
8
715
%
96
1.5
1.3
1.1
Open-Ended Lines
Number
29
2
2
0
33
%
88
6
6
0
Drains
Number
*
%
All
Equipment
Number
783
22
18
11
834
%
94
3
2
1
* Drains at this facility are enclosed
** Pump seals in benzene service have double mechanical seals
Sun Oil Data
VQC
Concentration
ppm hexane
0-200
201-1000
1001-10000
> 10000
TOTAL
EQUIPMENT TYPE
Pump Seals
Number
24
6
3
0
33
%
73
18
9
0
Compressor Seals
Number
0
%
Control Valves
Number
44
3
4
2
53
%
83
6
8
4
Other Valves
Number
635
9
8
6
649
%
98
0.1
0.1
0.1
Open-Ended Lines
Number
20
1
1
0
22
%
91
5
5
0
Drains
Number
r
%
All
Equipment
Number
723
19
16
8
766
%
94
2
2
1
-------
DPA Data
Table 11-3: Summary of Results: VOC Concehtration versus Occurrence Frequency;
Hydrodealkylation Unit, Sun Oil Company, Toledo, Ohio
VOC
Concentration
ppm hexane
0-200
201-1000
1001-10000
> 10000
TOTAL
Pump Seals
Number
15
6
6
3
30
%
50
20
20
10
Com
Mum
EQUIPMENT TYPE
pressor Seals
ber
0
%
Control Valves
Number
30
1
8
5
44
%
68
2
18
11
Other Valves
Number
338
31
29
29
427
- *>
10
79
7
7
7
Open-Ended Lines
Number
18
1
6
3
28
%
64
4
21
11
Drains
Number
*
%
All
Equipment
Number
401
39
49
40
529
%
76
7
9
8
Drains at this facility were enclosed
VOC
Concentration
ppm hexane
0-200
201-1000
1001-10000
> 10000
TOTAL
EQUIPMENT TYPE
Pump Seals
Number
7
7
4
3
21
*
33
33
19
14
Compressor Seals^
Number
0
F
Control Valves
Number
29
3
5
7
44
%
66
7
11
16
Other Valves
Number
306
30
24
33
393
%
78
8
6
8
Open-Ended Lines
Number
20
1
5
3
29
%
69
3
17
10
Drains
Number
^
%
All
Equipment
Number
362
41
38
46
487
%
74
8
8
9
-------
TABLE II-4. SUMMARY OF RESULTS MEASUREMENT REPRODUCIBILITY
BETWEEN TWO TEST TEAMS, SUN OIL CO., TOLEDO, OHIO
A = EPA Test Team
B = Sun Oil Test Team
VOC Number of Cases Number of Cases % of Readings
Concentration With Results in With Results NOT NOT in Same
Range the Same Range* in Same Range* Range
0-100
101-1000
1001-10000
>10000
109.6
45
53
43
13
14
18
6
1%
31%
34%
14%
Listing of Data Points With VOC >100QO That Had Different Result*
Team A Result Team B Result
>1000.0 8000
>1QQQO 5000
>10000 4000
>1QQOQ 4000
>10000 1QOO
>10000 3000
*EPA result used as reference.
-------
TABLE II-5: WEIGHT PERCENT COMPARISON OF
BENZENE CONTENTS:LIQUID SAMPLES
AND ASSOCIATED VAPOR LEAKS
Source Type
Control Valve
Pump
Valve
Valve
Valve
Valve
Valve
"Valve
Waste Water
Separator
Waste Water
Separator
Waste Water
Separator
Waste Water
Separator
Pump
Pump
Motor Valve
Valve
LIQUID SAMPLE
Sample
Number
404
405
431
432
433
434
435
414
425
426
427
428
429
, 430
Wt. % Bz
23.654
0.004
0.826
0.962
0.022
0.578
1.045
5.987
0.399
0.555
0.001
2.519
0.003
0.0
VAPOR SAMPLE
Sample
Number
403
402
407
408
409
410
411
412
416
415
421
422
417
418
419
420
8
Wt. % Bz
1.270
0.0
1.583
0.902
0.0
0.0
0.0
9.670
0.0
7.661
1.235
2.855
0.083
2.632
0.0
0.308
Bz
ppmv
5
0
6
7
0
0
0
524
0
14
21
2
2
131
0
1
Material
Beinq Handled
Extractor Recycle
Benzene Tower
Bottoms
Debutanizer
Bottoms
Debutanizer
Bottoms
Debutanizer
Bottoms
Merox Product
Stabilizer Bottoms
Heavy Reformate
Unit Feed
Forebay
Outfall
Forebay
Outfall
Reformate Tower
Bottoms
Hydrocracked
Gasoline
Heavy Aromatics
Xylene Tower Bottoms
BTX Raffinate
-------
III. PROCESS DESCRIPTION
The Sun Petroleum Products Company, Toledo, Ohio, refinery is an
integrated gasoline producing petroleum refinery. The units and equipment
tested were those which had the potential for benzene emissions. Most of
the testing was performed in the two units which process pure benzene, the
BTX extraction unit and the toluene hydrodealkylation (HDA) unit. The BTX
unit uses liquid-liquid tetraethylene glycol extraction to separate the
aromatics from an aromatics reformer heartcut. The aromatics are then fractionated
and the raffinate is sent to gasoline blending. The unit was about one year
old when tested. During the design, construction and startup of the unit
special care was taken to reduce equipment leaks. Process valves were repacked
with two to three times the normal packing, double seals were used in benzene
service, and all relief valves and process accumulator vessels were tied into
the flare header system.
The HDA unit was originally built in 1961 as a naphthalene unit and was
shut down in 1973. The unit was then modified and restarted as a 1 ton unit.
Sun plans to make several changes to reduce leakage in the HDA unit (i.e., retrofit
double seals), but these changes had not been made when the fugitive emissions
testing was performed.
Based on discussions with plant personnel both process units were operating
normally throughout the test period.
Both the BTX and HDA units had area monitoring systems manufactured by ARCAS.
Company literature is shown in Appendix D. The BTX monitors measure ppm benzene,
toluene and xylene sequentially through 15 points in the unit. The HDA
monitor also measures through 15 sample points but for only benzene and toluene.
Calibration testing of the BTX unit monitoring system showed this system was
not operating properly during the test period so these data have not been analyzed
in this report.
-------
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 daily at 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
1 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 concentrations.
The highest observed concentration was recorded on a field data sheet.
The chromatographic techniques used to analyze the grab samples of
vapors and liquids are described in Appendix A. Vapor samples were collected
in 100 cc gas-tight glass syringes. Liquid samples were collected in
500 cc - 1000 cc glass or metal containers, as appropriate.
10
-------
APPENDIX A
LABORATORY REPORT
-------
MEASUREMENTS OF
FUGITIVE VOC EMISSIONS
FROM A PETROLEUM REFINERY IN
TOLEDO, OHIO
Contract 68-02-2815
Work Assignment 27
Submitted to
/
U.S. Environmental Protection Agency
Emission Measurement Branch
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
Submitted by
Engineering-Science
7903 Westpark Drive
McLean, VA 22102
April 1979
-------
TABLE OF CONTENTS
SECTION I
SECTION II
INTRODUCTION
RESULTS
SECTION III ANALYTICAL PROCEDURES
FIELD TESTING
LABORATORY ANALYSIS OF LIQUID AND HEAD SPACE
SAMPLES
Page
1-1
II-1
III-l
III-l
III-3
APPENDIX A FIELD DATA
STANDARDS AND SAMPLE ANALYSES
APPENDIX B LABORATORY DATA SHEETS FOR LIQUID AND
HEADSPACE ANALYSES
LIST OF TABLES
TABLE II-l TOLEDO - FIELD SAMPLES
TABLE II-2 EPA - SUN OIL - LIQUID SAMPLES
TABLE I1-3 HEAD SPACE - WASTEWATER SAMPLES
II-3
II-6
II-8
-------
SECTION I
INTRODUCTION
The United States Environmental Protection Agency, Office of Air Quality
Planning and Standards (OAQPS) is currently investigating the magnitude and
nature of fugitive volatile organic carbon (VOC) emissions from petroleum
refineries for the purpose of recommending appropriate emission standards
for that industry. Engineering-Science was issued Task Order Number 24
under Contract Number 68-02-2815 to provide field testing capabilities for
development of fugitive emission data from a petroleum refinery.
The field test program was conducted at the Sun Oil Company's Toledo
Ohio facility during the period from November 13 through November 17, 1978.
The test program utilized two portable total hydrocarbon analyzers (Century
Organic Vapor Analyzer, OVA) and a Hewlett Packard 5830A gas chromatograph
(gc) equipped with dual flame ionization detectors. This report presents
only test results obtained with the gc.
The remainder of this report is divided into two sections as follows:
Section II - Summary of Results
Section III - Analytical Procedures
In addition, raw field data, example calculations, and laboratory data
are presented as appendices.
-------
SECTION II
RESULTS
The result of the syringe samples collected and analyzed during the field
test program are presented in Table II-l. Chromatograms were subdivided into
carbon number by retention times. The gc response for compounds of special
interest (aromatics) were extracted from the subdivisions and calculated in-
dependently from those groups. The electronic response for each group (C]_,
G£ . . C]_Q parafins, aromatics, and known olefins) was subtotaled and an
average response factor for each group applied to obtain a corrected instru-
ment response. These values were totaled to obtain total hydrocarbon count.
The weight percent per group was then determined and is presented in Table II-l
for field samples and Tables II-2 and II-3 for liquid and head space samples,
respectively. In addition, for the field samples, a total hydrocarbon con-
centration was determined by applying the averge instrument response as deter-
mined from the propane standard to the total corrected instrument response for
the sample. The table also presents the percent total reactive hydrocarbons
which was determined by subtracting the C^ and G£ weight percents from 100%.
This value assumes that all G£ found was ethane since ethane and ethylene
resolution was not possible with the analytical conditions used.
Table II-2 presents the results of the liquid sample analyses performed
in the ES McLean Laboratory. The weight percent values were determined in
the same manner used to calculate weight percent for the gaseous field samples.-
Total ppm was calculated by comparing the total corrected instrument response
for the sample to an average total instrument response for retention time
mixtures. The mixtures were pure hydrocarbon and, therefore, given a value of
1,000,000 ppm. Since this value is based on a single calibration point (106
ppm), it provides only an approximate estimate of the hydrocarbon content of
the samples.
Head space from the two wastewater samples (425 and 426) were also analyzed
by gc. The results of these analyses are presented in Table II-3. No total
ppm value was -determined since this value was not considered relevant to any
real conditions.
II-l
-------
Due to the complexity of the sample compositions for both field and
laboratory analyses, it was not possible to distinguish between olefins
and parafins. Only a few straight chain olefins were identified. These
are reported in the summary tables.
II-2
-------
TABLE II-l
TOLEDO - FIELD SAMPLES
VOC ANALYTICAL SUMMARY
SAMPLE NUMBERS
PARAFINS
CT
C2
C3
C4
C5
C6
c?
C8
Cg
CTO
AROMATICS
BENZENE
TOLUENE
XYLENES
F^S^i^isSi^s^s^S^x
'.^^^f^S^a^wS^teT--,
#7- HC%&"<»-' $&& V-i^f/^^'' <5^"-
PfeillSS^^^^ggv;
ETHYL BENZENE
MESITYLENE
OLEFINS
C2
C3
C4
C5
ce
TOTAL ppm 2
?a«S$f«^^^
K^VA&,l5U+-JT£ ^LrSiK-'.ii-f-.
TOTAL REACTIVE
HYDROCARBONS, %
^V-, ,,,_,/ " i^f--,- .">- t;':'';- (-^h*!* ' -"
4011
402 1
4031
4061
407
408
409
410
WEIGHT PERCENT
49.A23
14.177
2.032
7.292
14.630
3.709
24.840
3.357
21.470
2.378
2.226
24.413
3.662
66.083
11.461
14.461
7.995
4.739
1.186
1.803
6.458
11.009
14.349
8.123
6.434
0.548
1.275
5.765
15.866
17.231
5.784
2.567
11.465
0.116
35.428
10.989
18.101
51.639
6.581
7.244
8.113
1.876
8.737
V>='-'- !"«*,'.*£ ^'i--£**
28.441
21.320
Vi"3?3r£t-1 .^~^.\
*-ilt;^5^&;
««K:Tji«'*«jSM;- "^
0.153
0.420
1.270
64.707
^s^-r;^^"
Ss^-^^*^
^i^S^S^s^
'W*&«?r«i
1.583
11.150
25.649
',ffii-'aR3-**-feVi"
'^s^ss^i^
7.519
0.902
3.828
10.537
l$ii|S
7.702
j^^^^^^i^s-
""* i'J^S VWJK**i'>^:fe> '#"
2.724
2.497
jj/^Vwe?"'..^
f-^*-^^"^
:^:jj*%;.^t?
1.227
1.345
2,139
'sfes||sft
"'^r"-*.^-^^.. .'&
36.4
'-^«S&;L'-;.t^:
^»>«S?»!Pi:''
32,864
100
:"^.;;;;^r'^'
"'.A -*; '^j^ 3
2,482
' .^^"l^r^S!
^'-^ ^"tef S*)*^-*
97.622
^.^ji^-'^-ji
277
^"j^a!^*'*^^^-*;.
'.^g» ?S' ' t *^^^»^'^
33.917
Vr^^-'^r-' ^
^-^^iWi**^*^-1^':'-,,
0.767
11.224
4.539
2,098
"'S-.'^'avVt"*'^' j* %
--Aj:j-|3?-f*^'
100
^'-;;;cV>^:
4796
^.-r:,,",---f^,--g
Jif-l^g^
100.000
.^S^"'"?
53.423
0.046
20,416
v^^Z&i
- -.',/>y -. .:. -- '"
100
> 5,uV' ..;.- -,'
vv, - 'r ft . - --,^ ii.
1049
;?"'"!". ft*-' (''- -'^
£.:'~?fei; ~-'-:«
100
";'"^v -,;"»! ";
^Values obtained from a single analysis of the sample
PPM as Methane, determined from propane standard
II-3
-------
VOC ANALYTICAL SUMMARY
TABLE II-l (Cont.)
TOLEDO FIELD SAMPLES
SAMPLE NUMBERS
PARAFINS
Cl
C2
C3
C4
C5
C6
c?
C8
C9
ClO
AROMATICS
BENZENE
TOLUENE
XYLENES
ETHYL BENZENE
MESITYLENE
OLEFINS
C2
C3
C4
C5
C6
TOTAL ppm2
TOTAL REACTIVE
HYDROCARBONS, %
411
412
1.122
A. 604
2.407
26.411
0.118
0.031
1.981
15.305
10.678
2.507
0.723
1.914
413
415
416
417
418
WEIGHT PERCENT
7.927
34.478
1.563
21.490
9.670
29.231
25.606
2.236
100
^ilSSfesSSi
0.145
0.151
1.830
4.217
3.549
2.963
4.217
8.040
4.504
14.061
4.632
13.857
41.937
20.451
2.377
5.437
0.007
0.012
4.279
0.061
0.012
52.014
0.016
0.268
2.735
38.660
27.517
16.276
3.704
1.370
- 2.517
4191
43.681
7.661
17.410
22.575
8.681
7.047
4.264
1,670
100
32,492
100.000
0.083
28.418
W^^^^^^^-'l
15.116
2.632 .
3.037
0.704
'J$ J&jffiv&rf&Z
0.568
1.689
jfrvi*'..:'!';..';: i
SiStfe'sJS'
54.630
113
100
1,078
99.704
»^K* .^SftJr.ygJS^t'i:!''''
'.^'&''.$%$S>&£;
473
*fey'iP:f*fe;.V->fcv
Jflfsilsff
95.368
15,249
99.993
29,977
'V^^SPfffe
99.984
J;^K^|:'
1,296
^U;../;^-,*;*--*-
v~^v &;/; £*" "";
100
Values obtained from a single analysis of the sample.
ppm as methane, determined from propane standard.
II-4
-------
VOC ANALYTICAL SUMMARY
TOLEDO FIELD SAMPLES
SAMPLE NUMBERS
PARAFINS
cl
C2
C3
C4
C5
C6
C7
C8
C9
CTO
AROMATICS
BENZENE
TOLUENE
XYLENES
Sigp^llitiS
ETHYL BENZENE
MESITYLENE
OLEFINS
C2
C3
C4
C5
C6
TOTAL ppm2
TOTAL REACTIVE
HYDROCARBONS, %
*-,.
4201
4211
4221
423
4241
WEIGHT PERCENT
4.076
20.558
20.905
20.146
4.084
12.236
0.025
1.072
28.156
28.215
14.654
13.326
3.774
1.049
1.079
0.706
6.743
14.196
10.080
12.953
4.531
2.975
6.806
0.190
0.402
0.585
0.308
2.675
9.736
5.278
1.235
4.485
1.889
0.233
0.809
2.855
13.550
15.980
2.599
6.027
3.817
45.650
47.685
4.492
47.163
46.650
0.442
p^g|>
S^siie
%$&&£<
2.660
0.266
2,013
100
< *
10^,350
99.975
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100
-
8^07
100
'
778
100
-
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H£^X ^ifc?*'^
,.-.'..;?: ".'?.<':',. ;
Values obtained from a single analysis of the sample.
ppm as methane, determined from propane standard.
II-5
-------
VOC ANALYTICAL SUMMARY
VOC CONCENTRATIONS
TOLEDO FIELD SAMPLES
SAMPLE NUMBERS
401
402 403
406
407
408
409
410
PARAFINS.
ppm HC
1057
183
152
30
C3
33
8
C4
15
.1808
47
C5
1633
11
55
449
108
101
22
127
12
11
22
13
33
118
C8
39
138
38
35
11
2
784
19
14
14
55
AROMATICS
BENZENE
31
TOLUENE
1335
33
26
XYLENES
876
201
67
63
ETHYL BENZENE
MESITYLENE
15
17
41
OLEFINS
2727
108
36
TOTAL ppm v*
2138
32864
2482
277
2097
4794
20416
1048
TOTAL REACTIVE
HYDROCARBONS
Total ppmv as methane.
-------
VOC ANALYTICAL SUMMARY TOLEDO FIELD SAMPLES
VOC CONCENTRATIONS
SAMPLE NUMBERS
PARAFINS
C1
C2
C3
C4
C5
C6
c?
C8
Cg
CTQ
AROMATICS
BENZENE
TOLUENE
XYLENES
ETHYL BENZENE
MESITYLENE
OLEFINS
C?
C3
CA
C5
C6
TOTAL opmv*
TOTAL REACTIVE
HYDROCARBONS
r^'W£S3K-A
411
412
413
415
416
417
ppm HC
3
10
4
45
38
5
129
829
496
102
26
62
2
1
7
12
8
6
7
11
5
15
26
16
38
17
1
4
1
(0.3
108
1
(0.1
771
418
419
4
26
202
2307
1368
709
138
46
77
57
19
71
3
40
524
1357
1040
S?T J^^a^^^jB,
81
19
'&***G3$S$&£m^jJ!$£>
14
26
30
10
5
3
2
527
282
131
130
27
20
3
79
1672
32491
".~"-' -^-^"Ifr- '^"-'i *^-'"' '**i>£v>r*£:*~.'~
113
1080
473
15248
, '""""%
29976
fe«f.;2j
1296
IKW"
?&3&3^
* Total ppmv as methane.
-------
VOC ANALYTICAL SUMMARY
VOC CONCENTRATIONS
TOLEDO FIELD SAMPLES
SAMPLE NUMBERS
420
421
422
423
424
PARAFINS;
pptn HC
C3
37
(0.7)
C4
729
C5
16
584
(0.4)
69
?53
60
197
C8
51
49
C9
12
25
11
(0.2
(0.5)
AROMATIC
BENZENE
21
TOLUENE
66
53
52
XYLENES
25
24
48
45
ETHYL BENZENE
MESITYLENE
12
(0.3)
OLEFINS
C4
TOTAL ppm v*
2013
10351
314
808
778
TOTAL REACTIVE
HYDROCARBONS
* Total ppmv as methane.
-------
TABLE II-2
EPA - SUN OIL LIQUID SAMPLES
VOC ANALYTICAL SUWARY
SAMPLE NUMBERS
PARAFINS
CT
C2
C3
C4
C5
C6
c?
C8
Cg
CTQ
AROMATICS
BENZENE
TOLUENE
XYLENES
ETHYL BENZENE
MESITYLENE
OLEFINS
C2
C3
C4
C5
ce
TOTAL ppm
^fff:*fr^&.-^"S.f'-i!f~rff:-^if-,,K
i^^^f^&^fsm
TOTAL REACTIVE
HYDROCARBONS
* >*,
404
405
414
425
426
427
428
429
WEIGHT PERCENT
0.000
0.000
0.894
8.191
9.636
1.710
3.040
6.598
0.004
0.003
1.468
4.141
0.000
0.000
0.716
5.786
10.496
3.755
1.512
16.831
0.000
0.002
0.404
1.309
2.832
8.654
6.225
2.591
65.433
1.911
4.978
7.663
2.262
31.020
50.778
0.000
0.244
0.002
0.002
0.001
0.002
84 . 354
0.000
0.119
2.279
42.963
25.333
19 . 166
4.679
0.148
0.224
0.000
0.000
0.001
0.005
0.003
0.003
0.032
99.803
23.654
31.976
14.300
0.004
i2.075
41.855
ts^p^;
>3ff* -it ..-i.- £js
.!,->-'-*?-ri.rv^
iSigtliS*
10.450
5.987
26.837
22.781
.^^"^few
^g-jsa^^:
5.299
0.399
5.160
4.731
0.555
0.832
SIB"
2.260
^^^..t^\^, -'.i''~,~zi'
0.001
0.005
7.966
l^fe^P"?
5;?rSg:>e
7.422
2.519 .
2.461
0.108
T&£*}:%$ri&?
** i 'Xs^;*£9J*^f^/ *
'** ^X-v'; **&'£'' ^*e':~i-
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0.003
0.010
0.141
"'" ''^1^r'^-f'^~.-'.-
v..,...n *** j..>\'>.-fr>.
i?;^yi%;.;j
0.000
0 000
1000000
,»*«!SC5P*>ft*«-
100
1000000
;'1f!'^*"''-'!^«>''-^"'''5'₯.
;^,^-^^^:^
^v.^ 4.* -j -gsgjji"* *-r
100
i*-fV
1000000
:sf5£i%^§<
100
650000
s^^sf^siate
,3rJ'i?i?.**i3
100
t, * "*
4200
- *4*?", ,^~.«.^ 2 ^
;^^^:-^
100
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1000000
;. ; '*?£.' V>Zi";.rs f
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590000
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960000
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100
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II-6
-------
TABLE II-2 (Cont.)
EPA - SUN OIL LIQUID SAMPLES
VOC ANALYTICAL SUMMARY
SAMPLE NUMBERS
PARAFINS
CT
C2
C3
C4
C5
C6
C7
C8
Co
ClO
AROMATICS
BENZENE
TOLUENE
XYLENES
ETHYL BENZENE
MESITYLENE
OLEFINS
C2
C3
c*
C5
C6
TOTAL ppm
TOTAL REACTIVE
HYDROCARBONS
y *" * ts.-J.'-*^*!- - - ,>
f ""* V-^ *
430
431
432
433
434
435
WEIGHT PERCENT
0.000
0.727
19.161
25.465
10.604
3.214
30.889
0.610
4.963
4.366
0.826
3.824
8.156
^wiSfi'jS^.I?^^''
3.089
0.006
0.064
0.962
4.061
7.646
2.939
.. ...
0.022
0.006
0.004
0.029
0.101
0.186
1.535
0.578
1.356
0.647
0.229
1.045
5.751
15.861
4.510
£tgt£"'23p»*i'V;.. ,V; ;
i^^^-V^i -.,;-.=
^W*^^'**" ""*"'
100000C
100
*t<*r-$ift tjju "~;
*6 A »f~g* 1* -»>
*" *^** J** "**"
880000
100
-*&£. J»-
»'.~-f* s?"
1000000
100
306000
100
150000
99.999
:&-" ^-ri^'v^ *$*'\ '"'
885000
100
« > v" *
'-
I~*:^b^=?^I
/^^^-i-' ^ . ' v^<**£..';
II-7
-------
TABLE II-3
HEAD SPACE - WASTEWATEE. SAMPLES
VOC ANALYTICAL SIMMARY
SAMPLE NUMBERS
PARAFINS
Cl
C2
C3
C4
C5
C6
Cy
C8
C9
CID
AROMATICS
BENZENE
TOLUENE
XYLENES
ETHYL BENZENE
MESITYLENE
OLEFINS
C2
C3
C4
C5
C6
TOTAL ppm
TOTAL REACTIVE
HYDROCARBONS
"^ *"* "-NW
425
426
WEIGHT PERCENT
n.^7->
0.122
2.223
33.521
21.423
8.557
11.227
4.130
1.031
5.169
n ^fi7
0.161
1.094
4.722
3.515
1.157
3.038
1.311
0.667
73.955
sPi^K
:«881i
s^sftSa
0.756
3.389
1.556
n 17S
0.038
2.175
6.450
SUfe'
^Hsffi.
^^fe
*Wfc-:
4?;iuA3
-fe;*^
6.348
1.153
-
SSiS
« -r ^
99.505
* *~ *
99.275
- -»_*
p§p@
-v f
^li^w^
-
V^w^r^
**
^f:C^'-v."
'*-i\ ,;-
II-8
-------
SECTION III
ANALYTICAL PROCEDURES
FIELD TESTING
ES employed a Hewlett Packard 5830A dual FID gas chromatograph for deter-
mination of the composition of grab samples provided by the EPA test team.
Samples were collected in glass 100 cubic centimeter syringes. The gc was
equipped with a gas sampling valve and 1 cc sample loops. The valve inlet
was sealed with a septum. Samples were injected from the glass syringes
through the septum and flushed through the gas sample loops. A minimum of -
20 cc of sample was used to flush the valve prior to each sample injection.
After duplicate analysis of a single sample or standard, the gas sampling
valve was flushed for several minutes with zero grade air (total hydro-
carbon less than 1 ppm) prior to injection of the next sample. All samples
were analyzed on the same day as their collection. Between the time of
collection and sample analysis, samples were stored in an opaque container
to protect against component degradation.
The column used for the analysis was a 6 foot by 1/8 inch (outside
diameter) stainless steel column packed with 5% SP 1200/1.75% Bentone 34
on 100/120 mesh Supelcoport. The column was operated at 58°C for 15
minutes and temperature programmed to increase oven heat at a rate of
5°C per minute to a maximum temperature of 160"C. Compounds of primary
interest were aromatic hydrocarbons. Prior to conductance of the field
test, ES established retention times for approximately 30 compounds in-
cluding benzene, toluene, xylenes, ethylbenzene, straight chain and
branched paraffins through Cg and straight chain olefins through Cg.
These retention times were established under isothermal conditions at
58°C. Due to the rather lengthy time required to perform a single
isothermal analysis in the'field (approximately 100 minutes), it was
decided to utilize temperature programming. A mixture of eleven compounds
was used to re-establish retention times in the field.
III-l
-------
Instrument calibration was performed using propane and benzene standards.
The propane standards were 93.7, 987, and 100,000 parts per million in air.
At least one propane standard was run daily. Area counts as determined by
the electronic integrator were divided by the propane concentrations to obtain
a counts per ppm of propane value. Over the four day period and the 100,000
ppm standard range, the counts per ppm averaged 271.94 with a range of
254.4 - 287.7 and a standard deviation of 13.79. The maximum error was deter-
mined to be + 9.762. Propane standard data is presented in Appendix A.
Benzene standards were nonlinear during the first three days of field
testing. On the final day a linear response was obtained. The reason for
the nonlinearity was not successfully determined. The most probable expla-
nations for the nonlinearity are as follows:
1. Column leakage
2. Improper carrier/hydrogen/air mix
3. Condensation in sample valve system
All of these operating problems could have a similar affect on the sample
analysis as on the standard analysis. A leak in the carrier gas system would
also be expected to have an effect on the propane standard, which case was
not observed. The propane standard was linear in the range from 93.7 to
100,000 ppm.
Nonlinearity of the propane standard would also be expected if the air/
fuel/carrier mix was incorrect. Although it would probably be less severe
than the nonlinearity observed in the benzene standard, it is expected that
nonlinearity would be apparent when considering the range (93.7 - 100,000
ppmv) of propane standards run during the test period as compared to the
benzene standards (4.77 - 999 ppm).
The third possible explanation for the nonlinear benzene curve is con-
densation of benzene in the sample injection system. The gas sampling valve
and associated tubing used was not heated since samples were collected at
ambient temperature. When high concentrations of benzene and other heavy
compounds were injected, it is possible for some condensation to occur. How-
ever, the standard gas mixtures were relatively low concentrations and all of
III-2
-------
the internal valve parts were stainless steel. Thus it is difficult to assume
condensation as the sole explanation for nonlinearity. In all probability some
combination of the three factors mentioned may have resulted in the nonlinear
benzene response.
LABORATORY ANALYSIS OF LIQUID AND HEAD SPACE SAMPLES
Process stream and wastewater samples were collected during the field
test program and returned to the ES McLean Laboratory for analysis. Prior
to analysis the gc was checked for linear response using a series of liquid
dilutions of C^4, C^, and C^£ hydrocarbons. In the interim from the field
test program to the laboratory analysis, two modifications were made to the
system. First, the gas sampling valves were removed from the system to allow
on-column injection. Second, the carrier gas was changed from helium to
nitrogen since nitrogen is reported by the manufacturer to have a broader
linear range than helium. The resulting linearity check, showed good linear
response over the range from 20 to 20,000 ppm.
Liquid samples collected in the field were transported in ice to the
ES laboratory in McLean, Virginia. Samples were then refrigerated until
analysis was performed. Due to instrument linearity checks, liquid sample
analyses were not completed until February 16, 1979. Although samples were
sealed, protected from light, and refrigerated during the three month interim
from the time of collection, some sample degradation may have, occurred.
Prior to analysis., portions of the samples were gravity filtered through
Whatman Number 1 filter paper to remove particulate material. One microliter
aliquot was injected into a 200°C injection port. The column used for liquid
analysis was 10 foot by 1/8" stainless steel packed with 20% SP2100/0.1%
Carbowax 1500 on 100/120 mesh Supelcoport. The oven was maintained at 35CC
for 15 minutes then temperature programmed at a rate of 5CC per minute to
a maximum temperature of 165°C. All liquid samples were run in duplicate.
One cc headspace injection was made from the wastewater samples (Numbers
425 and 426).
Example calculations are presented in Appendix C. Field and laboratory
raw data is presented in Appendix A and B, respectively.
-------
APPENDIX B
FIELD DATA SHEETS
-------
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APPENDIX C
TEST LOG
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TEST LOG
11/13/78 - HDA OVA (2 analyzers)
vapor sample 1632-1647 Fenceline (2 analyzers)
11/14/78 - 0950-1015 BTX walkthrough 0 analyzer)
0930-1100)
) BTX OVA (2 analyzers)
1335-1524)
1610-1625 Fenceline (2 analyzers)
vapor and liquid samples
11/15/78 - 0915-1045)
1300- ) HDA OVA (-2 ana1rzers)-.
1610-1629 HDA walkthrough Q analyzer)..
vapor and liquid samples
11/16/78 - 1015-1042 BTX walkthrough 0 analyzer)
BTX 2nd level (2 analyzersJ_
BTX Unit: Tests of equipment w/>10000 for distance from
source and dilution probes.
vapor and liquid samples
11/17/78 - 1336-1444 BTX walkthrough (2 analyzers (4 runs)L
BTX monitor system test
vapor and liquid samples
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APPENDIX D
ARCAS VENDOR INFORMATION FOR THE
FIXED MONITORING SYSTEM
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ARCAS DIVISfU
ANACON INC.
ANALYTICAL EQUIPMENT
1-1
PMC 2000 SYSTEM OVERVIEW
The ARCAS PMC2000 Computer System is a bus oriented computer system
which has been built around the Motorola MC6800 microprocessor. The
heart of the system is the MPU module which contains the eight-bit
parallel microprocessor and the associated control circuitry- The
MC6800 microprocessor has 16 address lines used to address up to
65,536 words of memory and may directly address peripheral control
registers used for input/output (I/O) operations. The MPU has two
eight-bit accumulators, an eight-bit condition code register, a six-
teen-bit stack pointer register, a sixteen-bit index register, and
an interrupt system which includes vector addressing for interrupts
generated from restart/powerfail signals, software requests and re-
quests from external peripheral devices. Because an interrupt mask
bit is provided in the condition code register, interrupt nesting is
permitted which provides for priority interrupts.
The MPU module communicates to the other components in the system
over a bus or mother bo'ard. The mother board is constructed such
that each board in the system may occupy any position or slot on
the bus.
The System Software provided is a real time system with foreground/
background capability. The foreground processor includes:
Ch'romatograph control logic
Peripheral interrupt handlers
Analog input handlers
Alarm control I'ogic
Chromatograph cjalibration routines
Analog output handlers
The background processor includes:
List Option - which lists the options available in the background
_ processor.
Prog Display Option - which displays the function, number and values
required by the chromatograph.
Reports Option h which is used to obtain the latest analysis report
and shift reporft.
Peak Name Optioin - which allows the user to input or modify peak
names up to a maximum of 10 peaks (5 characters per peak).
Time-Date Optioti - which allows the user to enter or modify the tirr.
and date and up! to three shift times.
Test Pack Option - which contains several system hardware tests.
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ANALYZER
INTRODUCTION
These features are to be found in various models of the Analyzer sections of ARCAS pro-
cess gas chromatographs:
Double-walled ovens with inner layer of insulation; inside liner is stainless steel.
Air bath temperature control system using venturi air eductors and low-mass electrical
heaters.
Solid-state proportional temperature controllers.
A description of the main components mounted within or alongside the oven together with
some pertinent instructions are found in the following list. Detail sheets covering the ap-
propriate types or models pertaining to your specific instrument are inserted immediately
following this page.
Air Bath Temperature Control System
Carrier and Sample Flow
Sampleand Column Switching Valves
Detector Wiring Diagram (TC Models)
Sample Valves Brochure
Sample Valve Actuator Assembly
Sample Valve Flow Schematic
Solenoid Valves
CPI Tube Fitting (Instructions)
Case Purge Air Pressure Switch
tite.'
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F.I.D. DECTOR
-------
ARCAS PROCESS GAS
CHROMATOGRAPH
PROGRAMMERS
MODEL 405 PANEL MOUNT
SWITCH MEMORY
DIGITAL TIMER
MODEL 405 PANEL MOUNT
DATA ENTRY
DIGITAL TIMER
MODEL 1905
PANEL OR RACK MOUNT
SWITCH MEMORY
OR
DATA ENTRY
DIGITAL TIMERS
£1
j 5
*i"-'.-i* '<
MODEL 505
FIELD MOUNTED, AIR PURGED
PROGRAMMER,
SWITCH MEMORY OR
DATA ENTRY DIGITAL TIMER
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