study of source attribution of unsaturated hydrocarbons for ozone production in the...
TRANSCRIPT
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STUDY OF SOURCE ATTRIBUTION OF UNSATURATED
HYDROCARBONS FOR OZONE PRODUCTION IN THE
HOUSTON-GALVESTON AREA WITH THE EXTENDED
SAPRC99 CHEMICAL MECHANISM
Beata CzaderDaewon W. Byun
Department of Chemistry &Institute for Multidimensional Air Quality Studies (IMAQS)
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Propylene (Ton/Day)
MotivationThe metropolitan area of Houston is home to
the largest grouping of petrochemical industrial plants in the United States.
27.6 billion pounds of ethylene produced –
52% of national capacity
10.9 billion pounds of propylene produced –
63% of national capacity
TexAQS 2000 demonstrated the importance of HRVOC for ozone formation especially ethylene, propylene, 1,3-butadiene, and other butenes
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OBJECTIVES
Improve the resolution of the chemical mechanism – SAPRC99ext mechanism
Develop emission processing scheme for SAPRC99ext
Study the relationship between measured formaldehyde spikes and alkene
emissions
Study the differences in reactivity obtained with different chemical mechanisms
Compare AQM simulations based on different emissions inventories
APPROACH
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SAPRC99 and SAPRC99ext emission lumping
Speciation profiles
Ncpd
nnininpnpi MWreacallocxmfxmol
1,,,, /**
SAPRC99 SAPRC99ext
ETHENE ETHENE
OLE1
OLE2
PROPENE
BUTADIENE13
OLE1
OLE2
Gipson, G. L.: Speciation in Models-3/MEPPS and Models-3/SMOKE. 2001
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Reactions implemented in the SAPRC99ext mechanism
PROPENE + OH, O3, NO3, O(3P) BUTADIENE13 + OH, O3, NO3, O(3P)
Source: Carter, W., 2000. Documentation of the SAPRC-99 chemical mechanism for VOC reactivity assessment.
OLE1 → 73.2 (SAPRC99) → 85.0 (SAPRC99ext)
OLE2 → 75.8 (SAPRC99) → 77.0 (SAPRC99ext)
Molecular Weight
Source: Carter, W., 2000, Programs and Files Implementing the SAPRC-99 Mechanism and its Associated Emissions Processing Procedures for Models-3 and Other Regional Models.Carter, W., 2004, Documentation of speciation preprocessor programs for SMOKE.
R1 R2 SAPRC99 SAPRC99ext Propene/Butadiene
OLE1 OH 32.3*10-12 34.65*10-12 26.3*10-12
OLE2 OH 63.1*10-12 63.2*10-12 66.6*10-12
Reaction constant k(T)=A exp(-E/RT) at 298 K (cm3 · molec-1 · s-1)
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Modeling Data and Methodology
1. NEI 1999, SAPRC99, 2. NEI 1999, SAPRC99ext3. NEI 1999, CB-44. TEI 2000 (base4a.pto2n2), SAPRC995. TEI 2000 (base4a.pto2n2), SAPRC99ext6. TEI 2000 (base4a.pto2n2), CB-4
Simulated episode: Aug. 23 – Aug. 31, 2000
SMOKE 1.4 CMAQ 4.2.2
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The comparison of emissions for SAPRC-99 and SAPRC-99 extended
SAPRC99 SAPRC99 ext SAPRC99 SAPRC99 ext
65
60
55
50
45
40
35
OLE
1+P
RO
PE
NE
_sap
rc99
ext
65605550454035OLE1_saprc99 (kmol/hr)
TEI 120
100
80
60
40OLE
2+B
UT
AD
IEN
E13
_sap
rc99
ext
120100806040OLE2_saprc99 (kmol/hr)
TEI
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Emission rates with SAPRC99 and SAPRC99ext
60
50
40
30
20
10
PR
OP
EN
E [
kmo
l/hr]
8/23 8/24 8/25 8/26 8/27 8/28 8/29 8/30 8/31 9/1Date
NEI_SAPRC99ext TEI_SAPRC99ext
160
120
80
40
OLE
1 [k
mol/h
r]
8/23 8/24 8/25 8/26 8/27 8/28 8/29 8/30 8/31 9/1Date
NEI_SAPRC99 NEI_SAPRC99ext TEI_SAPRC99ext TEI_SAPRC99
National Emission Inventory NEI, 1999
Texas Emission Inventory TEI, 2000, base4a.pto2n2 (IMPUTED)
TEI, OLE1
NEI, OLE1
TEI, OLE1-PROPENENEI, OLE1-PROPENE
TEI, PROPENE
NEI, PROPENE
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Process Analysis results with SAPRC99ext
TEI
NEI
TEI
20.0 4.0 0.44.0
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CMAQ simulation results for ozoneSAPRC99 SAPRC99ext
NEI
TEI
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Comparison of simulation results with observed data
(at the surface)
La Porte side
HCHO
O3
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Williams Tower
HCHO data for HRM-3 obtained from P. K. Dasgupta
HRM-3
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Clinton80
60
40
20
0
Co
nc
[ppb
C]
8/23 8/24 8/25 8/26 8/27 8/28 8/29 8/30 8/31Date
observed NEI TEI
Clinton side Propene
100
80
60
40
20
0
Co
nc
[pp
bC
]
8/23 8/24 8/25 8/26 8/27 8/28 8/29 8/30 8/31Date
observed NEI TEI
Clinton side 1,3 - Butadiene
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Preliminary Conclusions
Among the anthropogenic emissions ethene and propene contribute most
to formaldehyde production. The contribution of 1,3-Butadiene and other
olefins is not significant.
With TEI, simulated concentrations of ethylene, propylene and other
olefins are higher than observed values, at the surface.
With NEI, olefin concentrations match observed values for some days of
the episode and are much lower for other (Aug. 23, 24, and 25).
Simulated values of 1,3-Butadiene match measured values at the surface,
with both TEI and NEI.
The differences in ozone production between SAPRC99 and SAPRC99ext
are around 1 ppb, as expected, however extending the SAPRC99
mechanism helps to identify the source-receptor relationship better.