&EPA
United States Office of Air Quality EMB Report No.81-OSP-9
Environmental Protection Planning and Standards July 1981
Agency Research Triangle Park NC 27711
On-Shore Production of
Crude Oil and Natural Gas
Sulfur Plants
Emission Test Report
Getty Oil Company
New Hope, Texas
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DCN 81-222-018-04-33 EMB Report No. 81-OSP-9
EMISSION TEST REPORT
S02 TESTING
AT THE
GETTY OIL NEW HOPE PLANT
NEW HOPE, TEXAS
Prepared by:
Jay R. Hoover
RADIAN CORPORATION
8501 Mo-Pac Boulevard
Austin, Texas 78759
Prepared for:
Winton Kelly
U. S. Environmental Protection Agency
ESED/EMB (MD-13)
Research Triangle Park, North Carolina 27711
EPA Contract Ho. 68-02-3542
Work Assignment No. 4
July 1981
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CONTENTS
Section Page
1 INTRODUCTION 1
2 SUMMARY OF RESULTS ' 2
3 PROCESS DESCRIPTION 5
4 LOCATION OF SAMPLING POINTS 8
5 SAMPLING AND ANALYTICAL METHODOLOGY H
6 QUALITY ASSURANCE/QUALITY CONTROL 14
7 COMPLETE RESULTS AND EXAMPLE CALCULATIONS 19
IX
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SECTION 1
INTRODUCTION
This report presents the results of testing for sulfur dioxide, reduced
sulfur, and nitrogen oxide emissions from the Glaus incinerator stack at the
Getty Oil New Hope Plant, near Mt. Pleasant, Texas. The testing was performed
by Radian Corporation on April 6 through April 13, 1981. This work was
funded and administered by the Emission Measurement Branch of the U. S.
Environmental Protection Agency. The results of this testing will be used to
develop New Source Performance Standards for on-shore production facilities.
The following sections present a summary of results, a description of
the process configuration, location of sampling points, the testing method-
ology, quality assurance/quality control procedures, and complete results and
example calculations. A full listing of the data and other supplemental
information are included as appendices.
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SECTION 2
SUMMARY OF RESULTS
This section presents a summary of the testing data at the Getty Oil
New Hope Plant. The complete test results and example calculations are
presented in Section 7. All of the supporting data sheets are included in
Appendix A.
The results for the S02, H2S, and TRS tests are summarized in Table 2-1.
This table also presents the liquid sulfur production data, the calculated
sulfur emission rate (S02 plus TRS), and sulfur recovery efficiencies.
Figure 2-1 graphically presents on a daily basis the sulfur recovery efficiency,
the S02 emission rate, and the liquid sulfur production.
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TABLE 2-1. SUMMARY OF RESULTS - GETTY OIL, NEW HOPE
S02 (ppra)
Date
4/8
4/9
4/10
4/11
4/12
TEST
PERIOD
Range
8,300-9,840
8,950-13,600
9,360-10,300
8,930-9,370
8,850-9,480
8,300-13,600
Average
8,950
10,520
9,950
9,080
9,150
9,517
H2S (ppm)
Range
426-662
446-925
333-1,800
331-402
144-408
144-1,800
Average
545
637
959
359
244
549
TRS
(ppra)
1,050
1,460
977
657
787
972
S02a..0ut
Stack (Ib/hr)
1,318
1,565
1,181
1,116
1,141
1,264
Sulfur(s)b Out
Stack (LTPD)
7.1
8.4
6.3
6.0
6.1
6.8
Liquid Sulfur
Make (LTPD)
144.7
146.2
123.2
113.0
113.0
128.0
Plant %
Efficiency
95.3
94.6
95.1
95.0
94.9
95.0
alncludes S02 plus TRS expressed as S02
Includes S02 plus TRS expressed as S
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Liquid Sulfur
Production
(LTPD)
150
140
130
120
110
Average Stack
SOa Emissions
(Ib/hr)
(includes S02
plus TRS)
1600
1400 .,
1200
1000
Sulfur
Recovery
Efficiency
96
95
94
93
9 10 11
April Test Date
12
Figure 2-1. Summary of S02 emissions and sulfur
recovery at Getty Oil's New Hope Plant.
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SECTION 3
PROCESS DESCRIPTION
The Getty Oil New Hope Plant is a gas processing facility that combines
natural gas liquids removal and gas sweetening. The feed gas to the plant is
from area gas wells. The natural gas liquids are removed, then the natural
gas is sweetened using an amine scrubbing unit. Sulfur is recovered using a
Glaus sulfur plant. The natural gas processed is higher in HaS than COz and
the acid gas feed to the Glaus plant is relatively high in HzS content (about
55 volume percent during the test period). The design capacity of the plant
is 60 MMSCFD of gas and the plant was treating approximately 27 MMSCFD of gas
during the test period. The Glaus plant has a capacity of about 150 long tons
per day (LTPD) of liquid, sulfur and was producing between 110 and 150 LTPD
during the test period.
A simplified schematic of the process is shown in Figure 3-1. The raw
gas stream is first treated to remove and recover the natural gas liquids
which are present. The acid gases in the gas stream are then removed by an
ethanolamine scrubbing unit. The hydrogen sulfide (HaS) released during
regeneration of the scrubbing liquor is processed in a Glaus sulfur plant
to recover elemental sulfur. The Glaus plant is a dual-train three-stage
catalytic unit, with the third catalytic reactor being common to both trains.
Liquid sulfur from the Glaus plant is collected in a below-ground storage
tank and sold. The acid gases remaining in the Glaus plant tail gas are
routed to an incinerator to convert the HzS to S02 prior to emission to the
atmosphere.
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Sweet _«_
Gas
Raw
Gas
Gas
Liquids
Separation
Sour Gas
A
11
S
0
B
E
Y
<
y-
s
T
R
I
P
P
E
R
Acid
Gas
CT»
Sampling
Point
Incinerator
Figure 3-1. Simplified flow diagram.
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Testing of the Glaus plant incinerator stack was performed to determine
the level of sulfur emissions, SOz, HaS, and total reduced sulfur (TRS), in
the stack. In addition, the liquid sulfur production was monitored to allow
estimation of the efficiency of the sulfur recovery plant.
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SECTION 4
LOCATION OF SAMPLING POINTS
Gas-phase samples were collected on the incinerator stack that services
the off-gases from the Glaus unit. Sampling was performed on the 180° sam-
pling platform located approximately 70 feet off the ground. Two three (3")
inch ports were available for sampling. The location and orientation of
these ports are shown in Figure 4-1.
Only two ports were required to perform a velocity traverse due to the
relatively small stack diameter (4.08 ft). A six-point traverse of each
diagonal was performed. The distances into the stack for point 1 is 2.2
inches; point 2, 7.2 inches; point 3," 14.5 inches; point 4, 34.5 inches;
point 5, 41.8 inches; and point 6, 46.8 inches. The proposed three-point
sampling technique used to collect the various gas-phase samples was eli-
minated in favor of a single-point of average velocity. Since the sampling
points are located greater than eight stack diameters from the nearest up-
stream or downstream disturbance and the velocity profile was relatively
constant across each diagonal, the gas stream should be homogenous at the
sampling points. Figure 4-2 shows the location of the sampling points with
respect to upstream and downstream stack disturbances.
All of the gas samples were collected through the W port. Samples were
collected at both point W2, which is 7.2 inches into the stack, and W4,
which is 34.5 inches into the stack. The field data sheets in Appendix A
indicate which point was used for each sample.
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STACK
PLATFORM
Figure 41. Location of sampling ports and
velocity traverse points
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Total Height
^ 245 ft.
Incinerated
Tail Gas
ID = 4.08 ft.
Sampling Platform
II Height ^ 70 ft.
Figure 4-2. Location of upstream and downstream
disturbances from sampling ports.
10
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SECTION 5
SAMPLING AND ANALYTICAL METHODOLOGY
To meet the objectives of this project, the following gas-phase parameters
were measured at the incinerator stack sampling platform:
volumetric gas flow rate,
molecular weight,
moisture content,
S02,
N0x>
HjS, and
total reduced sulfur (TRS).
In addition to the above parameters, the liquid sulfur production rate was
also monitored. Whenever possible, referenced source sampling and analysis
methods were used during testing at the New Hope Plant. Table 5-1 lists
the various parameters measured and the sampling and analysis methods used
to monitor these parameters. A description of the sampling and analytical
methodology is provided in Appendix B. .
TABLE 5-1. SAMPLING/ANALYSIS PARAMETERS AND METHODOLOGY
Parameter to be Measured Methodology
Volumetric Gas Flow Rate EPA Method 2
Gas-Phase Molecular Weight EPA Method 3
Gas-Phase HzO EPA Method 4
Gas-Phase SOz EPA Method 6
Gas-Phase NOX EPA Method 7
Gas Phase HaS EPA Method 11
Gas-Phase TRS EPA Method 16A
Liquid Sulfur Production No Reference Method
11
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The moisture content of the incinerator flue gas at the New Hope Plant
was determined using the methodology specified in EPA - Method 4. Attempts
were made early in the sampling program at the Warren Petroleum - Monument
Plant to collect both SOa and moisture samples with the same sampling train
(EPA Method 6). By weighing the impingers before and after sampling the mass
of water collected during sampling could then be related to the moisture con-
tent of the gas. But, because the gas volume collected during S02 sampling
was only 20 to 30 liters, the total mass of water collected during sampling
was 2.5 to 4.0 grams based on 15% H20 in the gas. Small losses (VL.O grams)
in the recovery of the collected HaO could have a large effect in the apparent
moisture content of the gas. To alleviate this problem, a separate sampling
train (EPA Method 4) was set Up by using larger impingers at a higher gas flow
rate to collect the H20 samples. This sampling arrangement allowed a larger
volume of gas CVL50 liters) and a larger mass of water (15 to 20 grams) to be
collected. Small losses in the recovery of the collected water did not have
as significant effect on the moisture determination.
The proposed three-point traversing technique used to collect the
various gas-phase samples was eliminated during this testing period. Instead,
a single point of average velocity was used to collect a majority of the gas-
phase samples. The decision to eliminate the three-point traverses was based
upon two facts. First, the sampling ports are situated approximately ten stack
diameters upstream from the nearest disturbance. Second, the velocity profile
is relatively consistent across each diagonal. To help insure that the gas
sample was homogenous by the time it reached the sampling ports, four sets
of gas samples were collected at a separate point within the stack. Analysis
of these gas samples for SOa, HaS, Oa, COa, and Na indicated that the con-
centration of these constituents were the same (within experimental error)
at both points in the stack.
Because of the very low particulate concentration in the incinerator
gas, a decision was made to eliminate the glass wool plug from the probe
liner. This decision eliminated the systematic placement and removal of a
12
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glass wool plug from a 850°F probe in-between SOz and HaS sample collection
runs. The glass plug is designed to remove particulate from the gas-phase
during SOa (EPA Method 6) and NOX (EPA Method 7) sample collection. However,
during H2S (EPA Method 11) and TRS (EPA Method 16A) sampling, the glass wool
plug is eliminated to minimize sorption losses of these gas species across
a particulate cake. By eliminating the glass wool plug, the probe did not
have to be removed from the stack in-between each sample. This minimized
the time that the extremely hot (850°F) probe had to be handled resulting
in increased personnel safety with a minimum of down time in-between runs.
13
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SECTION 6
QUALITY ASSURANCE/QUALITY CONTROL
A comprehensive quality assurance/quality control (QA/QC) program (Radian
DCN 81-222-018-04-09) was designed and implemented during this program. The
objective of this QA/QC program was to assess and document the precision,
accuracy, and adequacy of emission data developed during sampling and analysis.
A summary of the QA/QC results obtained during activities at the Good Hope
Plant are presented in this section. A brief discussion of the precision,
accuracy, and data capture are also presented in this section of the report.
Copies of the equipment calibration forms and reagent preparation/standardiza-
tion forms are presented in Appendix B.
ASSESSMENT OF DATA QUALITY
Table 6-1 summarizes the estimated and measured precision, accuracy,
and data capture for each of the parameters monitored at the Good Hope Plant.
The measured precision and accuracy for each of the parameters fall within
the original estimates. Deviations from estimated data capture are discussed
later in this section.
DISCUSSION OF QA/QC RESULTS
During this project, the precision and accuracy of a particular measure-
ment was determined by one or more of the following methods:
14
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performance audit,
system audit, and
quality control procedures.
Precision is defined here as a measure of mutual agreement among individ-
ual measurements of the same property. Precision can be qualified with respect
to the replicability and repeatability of a particular parameter. Replicability
is a measure of variability between measurements of the same parameter by the
same analyst using the same apparatus on the same day and in the same labora-
tory. Routine duplicate analyses were used to measure replicability during
the course of the project.
Repeatability is similar to replicability but requires that one or more
of the following be different:
analyst,
apparatus, or
the day.
Daily analysis of quality control standards by different analysts provided
a measure of repeatability.
Accuracy is defined here as the degree of agreement of a measurement (or
average of measurements of the same sample) with an accepted reference or true
value. The accuracy data presented in Table 6-1 represents the relative
accuracy of the measured value, X, with respect to the reference value, T,
of a field audit sample. Results obtained during the field performance audit
at the Monument Plant were also used to determine the accuracy of the data
collected at the New Hope Plant.
15
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TABLE 6-1. SUMMARY OF ESTIMATED AND MEASURED PRECISION, ACCURACY, AND DATA CAPTURE
FOR THE DATA COLLECTED AT THE NEW HOPE PLANT
Measurement Parameter
(Method)
Volumetric Gas Flow
Rate (EPA 1 and 2)
Molecular Weight
(Gas Partitioner)
H20
(EPA 4)
S02
(EPA 6)
NO
(EPA 7)
H2S
(EPA 11)
Total Reduced Sulfur
(EPA 16A)
Liquid Sulfur
Production
Estimated
(RSD)
20%
10%
11%
10%
10%
10%
51%
10%
Precision
Measured . i
t: ^Z . . . . - , , , , Accuracy
Replicability Repeatability *
(RSD) (RSD) Estimated2 Measured
20%" 20%" ± 11% ± 11% "
<2% <2% ± 25% <± 10%
in11 in" ± 10% ± 10% "
0.31% 0.76%/1.2%5 ± 20% <±0.5%
' 6 ± 20% <±2.5%
N/A7 N/A7 ± 20% N/A 7
0.31% 0.76%/1.2%5 ± 15% <±0.5%
± 5%
Data
Estimated
90%
90%
90%
90%
90%
90%
90% '
100%
Capture
Measured3
100%
100%
93%
100%
100%
100%
100%
100%
'Accuracy is based upon QA/QC Field Audit Performed at Monument Plant.
2Expected range for bias of method.
3The valid data percentage of the total tests required in the scope of work.
''The Monument Plant field performance audit showed no deviation from accepted procedure. Precision and accuracy
should be within the estimated values.
5Two different QC standards were used during the six day period. The 0.76% value is the mean RSD for analysis of
the first standard over a four day period. The 1.2% value is the RSD for the second standard analyzed the last
two days.
6NO precision cannot be properly calculated when all values are below the limit of quantitation (LOQ).
7Refer to the text.
RSD - Relative Standard Deviation
RSD Mean Relative Standard Deviation
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All definitions and procedures used in calculating precision and accuracy
were taken from Appendices A and C of the EPA document 600/9-76-005, Quality
Assurance Handbook for Air Pollution Measurement Systems, Volume I, Principles
(1).
Data capture can be calculated by several different techniques. The data
capture reported in Table 6-1 represents the valid data percentage of the total
tests required in the scope of work.
The following list summarizes the deviations, exceptions, and special
cases with respect to the precision, accuracy, and data capture data presented
in Table 6-1. These include:
The titrations of the peroxide impinger in the H2S trains are
included in the data base used in calculating precision for
analyses.
The precision and accuracy reported for the TRS analyses is
based on data from the S02 analyses since the analytical
procedure (BaCl2 titration, thorin indicator) is the same
and comparable titrant volumes were used.
Because of the lack of a suitably stable sulfide standard,
no sulfide QC standard was analyzed. Precision data for
H2S analysis is not presented because duplicate analysis
were not performed. The referenced analytical procedure
requires that the whole sample be titrated, precluding
duplicate analysis.
Accuracy data for H2S analysis are not presented. A "certified
standard" bottle of H2S gas is on order and will be used to
determine the accuracy of the methodology.
NO precision cannot be properly calculated when all values
are below the "Limit of Quantitation" (LOQ) .
The reported accuracy data for molecular weight, S02, NO , and
TRS reflect only the analytical phase of the measurement, as
discussed in Sections 3.2.8, 3.5.8, and 3.6.8 of EPA document
600/4-77-027b (2). The performance audit activities address
the sampling procedures.
17
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Both the precision and accuracy of the flue gas flow rate and
moisture determination are based upon the performance audit
performed at the Monument Plant. Since the field performance
audit showed no deviation from accepted procedure, both the
precision and accuracy are expected to lie within the estimated
values. Further information concerning the field systems audit
will be discussed in the separate QA/QC report.
Results obtained from the second moisture run performed on
April 10, 1981, appeared relatively high. Examination of the
impinger weight gains showed that the second impinger registered
an abnormally high weight gain. This data point has been classi-
fied as an outlier by means of the Dixon Criteria.
18
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SECTION 7
COMPLETE RESULTS AND EXAMPLE CALCULATIONS
This section presents the complete results and example calculations
for testing performed at the Getty Oil New Hope Plant. All of the support-
ing data sheets are included as Appendix A.
The results for the velocity, gas composition, and SOz tests are
shown in Table 7-1. This table also presents the calculated flow rates and
S02 emission rates. Table 7-2 presents the test results for HaS, TRS, and
NO along with the calculated emission rates.
X
This section also presents example calculations which show how the
test results were used to obtain flow rates, emission rates, and sulfur
plant efficiencies.
19
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TABLE 7-1. COMPLETE RESULTS: S02, FLOW - GETTY OIL
GETTY
DATE
4/8
4/9
4/10
4/11
4/12
OIL, NEW HOPE
RUN TIMEa 02
1
2
3
AVG
1
2
3
AVG
1
2
3
AVG
1
2
3
AVG
1
2
3
AVG
0822
1107
1450
0815
1030
1645
0820
1020
1310
0817
1011
1340
0807
1000
1240
5.6
4.9
5.8
5.4
5.2
5.6
3.5
4.8
2.1
2.4
4.6
3.0
5.1
5.3
5.4
5.3
5.6
5.4
5.2
5.4
CO 2
15.7
16.8
16.2
16.2
16.6
16.2
17.9
16.9
20.4
19.8
17.5
19.2
17.4
17.3
17.2
17.3
17.2
16.9
17.3
17.1
N2
75.8
75.3
74.9
75.3
75.5
75.7
75.7
75.6
74.1
74.3
74.7
74.3
74.1
74.5
74.5
74.3
74.1
74.5
74.7
74.3
STACK
TEMP(°F)
870
843
823
845
861
855
841
852
791
760
818
790
895
892
897
895
880
893
898
890
STACK VELOCITY
PRESS C'Hg) %H20 (FT/S)
29.95
29.95
29.95
29.95
29.92
29.92
29.92
29.92
30.12
30.12
30.12
30.12
30.03
30.03
30.03
30.03
29.99
29.99
29.99
29.99
26.30
26.70
26.70
26.60
26.10
27.00
29.30
27.50
31.00
31.00
26.90
29.60
25.90
26.70
26.20
26.30
27.00
26.60
27.10
26.90
58.2
56.5
54.7
56.5
58.9
58.3
55.5
57.6
45.5
44.3
49.4
46.4
50.5
50.9
51.7
51.0
50.8
51.3
51.9
51.3
FLOW
(ACFM)
45700
44300
42900
44300
46200
45700
43600
45200
35700
34700
38800
36400
39600
39900
40600
40000
39800
40300
40700
40300
FLOW
(DSCFM)
13200
13000
12800
13000
13400
13200
12300
13000
10300
10300
11600
10700
11300
11300
11500
11400
11300
11400
11400
11400
S02
(ppm.dry)
9840
8300
8700
8950
8950
9010
13600
10520
10300
10200
9360
9950
8930
8930
9370
9080
8850
9480
9120
9150
S02
(Ib/hr)
1310
1090
1130
1180
1220
1210
1690
1370
1070
1060
1100
1080
1020
1020
1090
1040
1010
1090
1050
1050
FOOTNOTES;
a - Time reported is when velocity profile was begun.
b - DSCFM at 60°F and 14.7 psia
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TABLE 7-2. COMPLETE RESULTS:
REDUCED SULFUR, N0x~ GETTY OIL
GETTY
DATE
4/8
4/9
4/10
4/11
4/12
OIL, NEW
RUN
1
2
3
AVG
1
2
3
AVG
1
2
3
AVG
1
2
3
AVG
1
2
3
AVG
HOPE
TIME
0822
1107
1450
0815
1030
1645
0820
1020
1310
0807
1000
1240
0807
1000
1240
FLOW
(DSCFM)
13200
13000
12800
13000
13400
13200
12300
13000
10300
10300
11600
10700
11300
11300
11500
11400
11300
11400
11400
11400
H2S
Cone ,ppm
426
548
662
545
489
925
689,446
637
1800
745
333
959
402
344
331
359
408
144
179
244
b
Ib/hr
57
72
86
72
66
124
71
87
188
77
39
101
46
40
38
41
47
17
21
28
TRSb
Cone ,ppm
1050
1050
1460
1460
977
977
657
657
787
787
Ib/hr
138
138
195
195
101
101
76
76
91
91
Cone ,ppm
13.0.
<3.0d
<3.0
<6.3
13.0
<3.0
<3.0
<6.3
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
N0xc
Ib/hr
<0.6
<0.6
<0.3
<0.3
<0.3
FOOTNOTES :
a - Time reported is when velocity profile begun
b - Lb/hr expressed as equivalents of SOz
c - Lb/hr expressed as equivalents of N02> all three
d - Detection limit is 3ppm, averaged in as 3ppm
NO samples taken during Run 3,
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EXAMPLE CALCULATIONS
FLOW RATES
Actual Cubic Feet per Minute (ACFM)
ACFM = Velocity x Stack Cross - Sectional Area
Example: Based on 4/8 averages -
2
ACFM = 56.5JIt_ x 4.08(ft) x II x 60 sec
sec 4 min
ACFM = 44,300 ft3/min
Dry standard cubic feet per minute (DSCFM) @ 60 °F and 29.92 in.Hg
APTTM -sr Barometric Pressure Standard Temp /.mole N
£\\jl; Li J\. -i-t-M "*-» tm " I -*- f
Standard Pressure Stack Temp. I fraction
H20
Example: Based on 4/8 averages-
29-95 (in.Hg) 520 ( R)
= 44 SOOCACFM^ x
^.juiHAUfM) x 29.92(in.Hg) 1305
DSCFM = 13,000 ftVmin
EMISSION RATES
Emission Rates- S02, NOX, HaS, TRS
. . r, . Concentration of Compound (ppm,dry) r.o^T-.v,
Emission Rate = rr-g -c *" x DSCFM x
compound mole wt
molar volume
Example: Based on 4/8 averages-
~ T, 8950 (ppm S02,dry) -,-, nnr. ^r,^, 64 Ib SQg
S02 Emission Rate = i-t-i- u~ x 13,000 DSCFM x x
106 379 SCF
60 min
hour
S02 Emission Rate = 1180 Ib/hr
Note: H2S and TRS Emission Rates are expressed as equivalent SOa;
NOX Emission Rate is expressed as N02;
Total S02 Emission Rate is the sum of S02 and TRS Emission Rates
22
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SULFUR PLANT EFFICIENCY
_, t _,..,. . Sulfur Recovered x 100%
Plant Efficiency = -,* "^ j;^. .. ,
J Sulfur Recovered 4- Emitted
where:
Sulfur recovered = liquid sulfur production (LTPD)
Sulfur emitted = SOZ + TRS Emission Rates (expressed as
elemental sulfur) (LTPD)
Example: based on 4/8 averages--
Plant Efficiency =
144.7 LTPD x 100%
144 7 (LTFD) I T( 118° + 138 " X x~2 lbs x LT x 24 hr1
144.7 (LTPD) +L hr x 64 lb SQ2 x 224Q lb x day J
Plant Efficiency = 95.3%
23
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