Basis for Emission Calculation from Flare Systems

Scot Smith
Director Flare Division
Zeeco, Inc.

Ben Pettys
Design Engineer Flare Division
Zeeco, Inc.









Abstract: In 1983, the Chemical Manufacturers Association (CMA) sponsored a study in
an attempt to define emission factors for flare systems. The study encompassed several
variables including the lower heating value of the gas, relief gas flow rate, air assist
rate, and steam assist rate. Emissions were continuously monitored by a sample probe
located above the flare flame to analyze the concentrations of carbon dioxide, carbon
monoxide, total hydrocarbons, sulfur dioxide, nitrogen oxides, and oxygen. The US
Environmental Protection Agency (EPA) published the AP-42 guideline for flare system
emissions, citing values that are essentially averages considering all of the CMA testing
data. Unfortunately, companies using the AP-42 data as their guideline for permitting
elevated flares could be citing values that are far from accurate, considering the wide
range of conditions tested in the CMA study. This paper will examine the original CMA
test data, discuss possible variations between the testing from 1983 and modern flare
system designs and operation, and identify the applicable conditions for employing the
various published factors for flare emissions.
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The concern for industrial emissions of pollutants and their effect on the environment
has been ever increasing since the 1950s. The emissions of carbon monoxide (CO),
nitrogen oxides (NO
x
), sulfur dioxide (SO
2
), particulate, and smoke have been
considered to have the greatest impact on air quality. Beginning in the 1970s and
through the early 1980s, elevated flare stacks were viewed as environmentally
problematic due to the highly visible flame and smoke. The EPA proposed to eliminate
flares as a viable device to control volatile organic compound (VOC) emissions from
refineries and chemical plants. To prevent flare systems from being excluded as an
option for destroying industrial emissions, the Chemical Manufacturers Association
(CMA) sponsored a study in 1983, primarily to determine the combustion efficiency of
flares. Several tests were performed for non-assisted, steam-assisted and air-assisted
flares in an effort to encompass the wide range of operating conditions defined by
normal industrial applications. Variables involved for both air assisted and steam
assisted flares included the relief gas flow rate, lower heating value (LHV) of the flare
gas, and air or steam assist rate. Testing was completed utilizing 100% propylene to
model high LHV flare gas scenarios and propylene diluted with nitrogen to represent
low LHV flare gas scenarios. The emission concentration of CO, NO
x
, SO
2
, carbon
dioxide (CO
2
), oxygen (O
2
), and total hydrocarbons (THC) was continuously monitored
by a sample probe located above the flare flame. The testing results concluded that an
elevated flare with an open flame had a combustion efficiency of at least 98% when
operated correctly. The EPA included all CMA testing to determine elevated flares have
a combustion efficiency of 98% however, if 40 CFR 60.18 parameters are followed, the
combustion efficiency will increase above 99.5%. These results were published and
utilized as a basis by the US Environmental Protection Agency (EPA) to develop the 40
CFR 60.11 to 60.18 regulations as well as the AP 42 Chapter 13.5 emission factors.
The EPA 40 CFR 60.18 guidelines use variables such as flare type, presence of a
continuously lit pilot, LHV of the flare gas, and the exit velocity of the gas to determine
if the flare is operating at the minimum 98% destruction efficiency. Once the flare is
operating within these constraints, emission factors presented in AP 42 Chapter 13.5
can be used to estimate the emissions of CO, NO
x
, unburned hydrocarbons (UHC), and
soot from the flare. The EPA developed and published the AP 42 document as an
emissions guide for flares used to control VOCs. These emission factors are an average
of applicable CMA test data. While AP 42 emission factors account for exit velocity,
lower heating value of the flare gas, and flare type, these values suggest emission rates
from elevated flares do not differ across the wide range of industrial applications. This
generalization ultimately causes estimated emission rates to be substantially different
for particular applications. As a result, the Texas Natural Resource Conservation
Commission (TNRCC) reviewed the original CMA test data in 1994 and published
emission factors that apply to certain flare types and lower heating values.
This paper will explain how NO
x
and CO emission factors were calculated by the EPA
and TNRCC, as well as discuss possible modifications to emission factors in an effort to
better represent actual flare emissions.
CMA Test Setup
As previously discussed, propylene was utilized as flare gas and diluted with nitrogen to
decrease the lower heating value of the gas. The flow rate for testing ranged from as
low as normal purge conditions and to as high as 703 SCFM. The study was completed
to establish a wide range of tests similar to operating conditions for common industrial
applications. Throughout testing, the air-assisted flare had a 4 gas riser and the steam
assisted flare used an 8 gas riser. This testing provided additional data to estimate
emissions; however, the results may not apply to the wide range of applications that
include flare design, tip exit area and relief gas composition. When considering these
variables, the actual emission rate may differ from the data obtained by CMA testing.

Development of Various Emission Factors

Emission factors published by the EPA and TNRCC are based on data obtained from
CMA testing performed in 1983. The assumption was made that when complete
combustion takes place, every mole of propylene is burned and three moles of carbon
dioxide is produced. The chemical reaction assuming complete combustion is shown
below:
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The molar relationship between propylene and carbon dioxide was then converted on a
mass basis using the molecular weight of propylene and carbon dioxide as shown
below:
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In the Flare Efficiency Study published by the CMA in 1983, an equation was developed
to determine an emission factor (E
NOx
) based on measured concentration levels of NO
x

and CO
2
. This relationship is shown below:

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Where:
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Methods discussed above could be applied to estimate CO emissions using the
measured concentration of CO and CO
2
from CMA testing. This was accomplished by
replacing the concentration level and molecular weight of NO
x
from the equation shown
above with the concentration level and molecular weight of CO. The relationship for the
emission rate of carbon monoxide is shown below:

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The emission factors for NO
x
and CO were calculated by applying the relationships
above for all tests using data within the statistical summary of the CMA study with
results shown in Table A-1 of Appendix A.




Development of TNRCC Emission Factors
In 1994, the TNRCC published emission factors primarily based on statistical data from
the original study performed by the CMA and EPA in 1983. To achieve higher accuracy
for estimating actual emissions from elevated flares, the TNRCC emission factors
accounted for the flare type and lower heating value of the relief gas. The emission
factors developed by the TNRCC are shown below in Table 1.



Upon reviewing the statistical data collected during the CMA testing, the emission
factors shown in Table 1 reflect an average of the derived NO
x
and CO emission factors
pertaining to the flare type and lower heating value of the relief gas. When calculating
the emission factors for steam-assisted flares relieving a low Btu waste gas and air-
assisted flares relieving a high Btu waste gas, all test data collected during the CMA
testing was included in the average of the derived emission factors.
In order to calculate emission factors for the remaining categories, multiple tests had to
be disregarded due to various reasons. For instance, during testing in the high Btu
steam-assisted category, the emission probe was placed into the flare flame during test
67, resulting in a substantial increase in the concentration level of both THC and carbon
monoxide. During tests 61 and 55, it was noted that the flare was capped by the assist
steam, contributing to destruction efficiencies well below 98%. Omitting tests 67, 61
and 55 from the high Btu steam-assisted waste gas data, the average of the derived
NO
x
and CO emission factor of the remaining tests resulted in the values shown above
in Table 1.
To calculate the emission factor for air and non-assisted flares relieving low Btu waste
gas, certain CMA test data were excluded in the calculation performed by TNRCC. Upon
detailed review of the CMA test data, one possible method for calculating the emission
factors in Table 1 entails disregarding tests 66, 29, 29a, 29b, and 62. Reasoning for this
assumption may be due to the lower heating value of the relief gas being below 184
Btu/SCF. However, data from test 33 appears to be included in the overall average
1ype WasLe Cas nCx lb/MM 8Lu of WasLe Cas
SLeam-AsslsLed Plgh 8Lu (>1000/scf 0.0483
SLeam-AsslsLed Low 8Lu (192-1000/scf) 0.0680
Alr and non-AsslsLed Plgh 8Lu (>1000/scf 0.1380
Alr and non-AsslsLed Low 8Lu (184-1000/scf) 0.0641
0.2733
0.3496
CC lb/MM 8Lu of WasLe Cas
0.3303
0.3463
1able 1. Lmlsslon facLors developed by Lhe 1n8CC for nCx and CC
emission factor and should not be applicable since the lower heating value of the flare
gas is 83 Btu/SCF. Once this test point is excluded from the overall average, the
emission factors for NO
x
and CO are 0.0645 and 0.4989 lb/MM Btu, respectively.

Development of EPA AP 42 Emission Factors
According to EPA AP-42 Chapter 13.5, emission factors were developed based on data
obtained during the 1983 CMA testing, which included steam-assisted flare tests with
gas exit velocities between 130 and 3,750 ft/min and air-assisted flare tests at gas exit
velocities between 617 and 13,087 ft/min. It is also stated that the EPA established that
steam-assisted and air-assisted flares could attain destruction efficiencies greater than
98% when the LHV of the flare gas is at least 300 Btu/SCF. The emission factors
published by the EPA for NO
x
and CO are shown below in Table 2.



Since the emission rate of NO
x
is independent of combustion efficiency, all CMA tests
were included in the average of the derived NO
x
factor taken by the EPA. This resulted
in the NO
x
emission factor presented above in Table 2. In order to determine the CO
emission factor published by the EPA, an assumption was made that CMA tests having a
destruction efficiency less than 98% could be excluded. When this assumption is
applied to the CMA test data, the average of the derived CO emission factors for the
remaining tests resulted in the value presented above in Table 2.





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Conclusion
To estimate emission rates for carbon monoxide and nitrogen dioxide based on CMA
test results, variables such as the LHV, exit velocity and flare type must be considered.
These variables were considered by both the EPA and the TNRCC. However, the
discrepancy between the published emission factors has caused some companies to
permit elevated flares using AP 42 guidelines citing values that are not representative of
actual emissions. In order to address this issue, supplemental testing must be
performed that considers additional variables to determine emission rates for current
industrial applications.


















References
1. AP 42, Fifth Edition, Compilation of Air Pollutant Emission Factors, Volume 1:
Stationary Point and Area Sources, U.S. Environmental Protection Agency,
Research Triangle Park, NC, January, 1995.
2. Flare Efficiency Study, EPA-600/2-83-052, U.S. Environmental Protection Agency,
Cincinnati, OH, July 1983.
3. Technical Guidance Package for Chemical Sources: Flare Sources, Texas natural
Resource Conservation Commission, Austin, Texas, November 1994.



















Appendix A

1ype
1esL
no.
PeaLlng value
8Lu/SCl
nC
x
ConcenLraLlon
ppm
CC
ConcenLraLlon
ppm
CC
2
ConcenLraLlon
ppm
uerlved nC
x
Lmlsslon lacLor
lb/MM 8Lu
uerlved CC
Lmlsslon
lacLor lb/MM
8Lu
CL
1 2183 3.09 3.8 7,032 0.0680 0.0836 99.96
2 2183 2.16 8.3 4,719 0.0710 0.2793 99.82
3 2183 3.46 13.8 8,139 0.0638 0.2623 99.82
4 2183 1.96 73.3 6,616 0.0439 1.7631 98.80
8 2183 1.43 61.1 3,400 0.0416 1.7348 98.81
7 2183 1.62 7.9 3,224 0.0481 0.2343 99.84
3 2183 2.09 4.1 6,113 0.0330 0.1040 99.94
67 2183 3.77 n/A 3,738 0.1336 n/A n/A
17 2183 1.00 6.1 3,493 0.0444 0.2708 99.84
30 2183 0.30 16.7 4,220 0.0184 0.6137 99.43
36 2183 0.38 7.8 3,120 0.0288 0.3877 99.70
61 2183 1.32 398.4 6,273 0.0326 9.8493 82.18
33 2183 0.38 171.0 2,012 0.0293 13.1807 68.93
37 294 2.68 3.0 6,943 0.0398 0.1117 99.90
11 - 3.69 7.1 3,269 0.1086 0.2090 99.83
11a 303 3.31 4.7 6,677 0.0769 0.1092 99.93
11b 342 4.17 8.6 8,138 0.0793 0.1633 99.83
11c 364 4.00 11.6 8,210 0.0736 0.2191 99.82
39 - 1.41 49.9 3,413 0.0404 1.4297 98.49
39a 192 1.30 62.1 3,373 0.0362 1.7273 98.11
39b 232 1.62 23.4 3,090 0.0494 0.7739 99.32
60 298 0.99 28.3 3,683 0.0417 1.1910 98.92
31 309 0.37 34.1 3,347 0.0264 1.3800 98.66
16 - 1.87 7.7 4,039 0.0714 0.2942 99.73
16a 339 1.39 6.1 3,236 0.0666 0.2923 99.74
16b 408 2.42 9.6 3,291 0.0709 0.2814 99.73
16c 319 1.37 7.3 3,419 0.0712 0.3311 99.74
16d 634 2.28 7.9 4,438 0.0793 0.2748 99.78
34 209 3.00 6.8 7,113 0.1090 0.1482 99.90
23 267 3.90 4.3 8,463 0.1081 0.0824 100.01
32 268 0.68 16.1 2,622 0.0402 0.9323 98.82
33 209 2.83 23.9 3,741 0.0764 0.6436 99.40
26 481.6 3.34 3.3 6,270 0.1321 0.1360 99.97
63 139.0 2.40 20.3 4,878 0.0763 0.6434 99.37
28 137.0 8.16 3.2 6,078 0.2082 0.0817 99.94
31 22.7 4.02 27.9 4,368 0.1363 0.9472 99.17
66 138 0.97 129.4 2,432 0.0619 8.2317 61.94
29 - 1.06 180.9 2,179 0.0734 12.8732 61.60
29a 168 1.09 146.6 1,329 0.1106 14.8696 33.14
29b 146 1.04 213.9 2,808 0.0374 11.8137 63.60
64 282 1.24 8.6 3,282 0.0386 0.4064 99.74
62 133 0.68 90.2 3,076 0.0343 4.3477 94.18
63 289 1.37 19.9 4184 0.0382 0.7376 99.37
33 83 0.74 13.8 1837 0.0618 1.3193 98.24
32 - 1.73 22.7 3702 0.0733 0.9310 98.87
32a 294 0.63 12.2 1761 0.0333 1.0744 98.91
32b 228 2.39 28.8 4811 0.0770 0.9284 98.86
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