Assessing Atmospheric Emissions from an Amine based CO2 Post-combustion Capture Processes

64 Pages·2014·2.45 MB·English

ENERGY FLAGSHIP

Assessing Atmospheric Emissions from an
Amine-based CO Post-combustion Capture
2
Processes and their Impacts on the
Environment – A Case Study

Volume 2
Atmospheric chemistry of MEA and 3D air quality modelling
of emissions from the Loy Yang PCC plant
Final Report

Merched Azzi, Dennys Angove, Ian Campbell, Martin Cope, Kathryn Emmerson, Paul Feron,
Michael Patterson, Anne Tibbett, Stephen White
May 2014
Global Carbon Capture and Storage Institute (Global CCS Institute)
Energy Flagship
Citation
Azzi M., Angove D., Campbell I., Cope M., Emmerson K., Feron P., Patterson, M., Tibbett A., White, S.
(2014).
Assessing Atmospheric Emissions from Amine based CO PCC Process and their Impacts on the Environment
2
– A Case Study. Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from
the Loy Yang PCC plant. CSIRO, Australia.
Copyright and disclaimer
© 2014 CSIRO To the extent permitted by law, all rights are reserved and no part of this publication
covered by copyright may be reproduced or copied in any form or by any means except with the written
permission of CSIRO.
Important disclaimer
CSIRO advises that the information contained in this publication comprises general statements based on
scientific research. The reader is advised and needs to be aware that such information may be incomplete
or unable to be used in any specific situation. No reliance or actions must therefore be made on that
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information or material contained in it.
Contents
List of Abbreviations ..................................................................................................................................... iv
Acknowledgments ......................................................................................................................................... v
Summary ....................................................................................................................................................... vi
Project Component 2: Experimental and modelling study of the photo-degradation of monoethanolamine
(MEA) in a mixed VOC/NOx system 1
1 Introduction .................................................................................................................................... 4
1.1 Background ........................................................................................................................... 4
1.2 Objectives ............................................................................................................................. 5
1.3 Project Description ............................................................................................................... 5
2 Experimental and Modelling ........................................................................................................... 6
2.1 Experimental ......................................................................................................................... 6
2.2 Mechanism overview ............................................................................................................ 8
3 Results and Discussion .................................................................................................................... 9
3.1 MEA results ......................................................................................................................... 10
3.2 Comparison of MEA with PZ and AMP ................................................................................ 11
3.3 Analytical results ................................................................................................................. 11
4 Mechanism Modelling ................................................................................................................... 13
4.1 VOC-only (NOx+VOC) experiments ..................................................................................... 13
4.2 MEA+NOx+VOC experiments .............................................................................................. 18
4.3 PZ+NOx+VOC experiment ................................................................................................... 24
4.4 AMP+NOx+VOC experiments.............................................................................................. 24
5 Summary of findings ..................................................................................................................... 28
Project Component 3: Modelling the potential impacts of emissions from the Loy Yang power plant
retrofitted with MEA-based PCC plant 29
1 Introduction .................................................................................................................................. 30
2 Model Components ....................................................................................................................... 31
3 Model Performance ...................................................................................................................... 35
4 PCC Scenario Modelling ................................................................................................................ 38
4.1 Ozone .................................................................................................................................. 41
4.2 Sulfur Dioxide ...................................................................................................................... 42
4.3 Nitrogen Dioxide ................................................................................................................. 42
4.4 PM2.5 .................................................................................................................................. 42
4.5 Monoethanolamine ............................................................................................................ 47
4.6 Ammonia ............................................................................................................................. 47
4.7 Nitrosamines and Nitramines ............................................................................................. 47
5 Conclusions ................................................................................................................................... 52
References .................................................................................................................................................. 53
Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant | i
Figures

Figure 1. Oxazol-type compounds identified or tentatively identified from MEA+NOx+VOC and PZ+NOx
experiments ................................................................................................................................................ 12
Figure 2. Low NOx-VOC (experiment 729) experimental and modelled data ............................................ 14
Figure 3. Low NOx-VOC (experiment 740) experimental and modelled data ............................................ 15
Figure 4. High NOx-VOC (experiment 742) experimental and modelled data ........................................... 16
Figure 5. High NOx-VOC (experiment 744) experimental and modelled data ........................................... 17
Figure 6. Changes to initial CSIMEA mechanism in edited model .............................................................. 20
Figure 7. High MEA, low NOx-VOC (experiment 761) experimental and modelled data ........................... 21
Figure 8. High MEA, low NOx-VOC (experiment 771) experimental and modelled data ........................... 22
Figure 9. High MEA, high NOx-VOC (experiment 766) experimental and modelled data ......................... 23
Figure 10. Low PZ, low NOx-VOC (experiment 805) experimental and modelled data ............................. 25
Figure 11. Low AMP, low NOx-VOC (experiment 809) experimental and modelled data ......................... 26
Figure 12. High AMP, low NOx-VOC (experiment 811) experimental and modelled data ........................ 27
Figure 13. Schematic diagram summarising the GCCSI modelling system. Note VOC -volatile organic
carbon; bVOC biogenic component of the same; EC- elemental carbon; OC- organic carbon; NO oxides
x
of nitrogen; NH ammonia; SO sulfate. ..................................................................................................... 32
3 4
Figure 14. Model domains used to (9 km grid spacing) resolve emissions from the Port Phillip and
Latrobe Valley airsheds; (3 km grid spacing) Latrobe Valley; (1 km grid spacing) near-field region around
the Loy Yang power stations. ..................................................................................................................... 33
Figure 15. Example of the model output from the 9 km spaced domain which includes the Port Phillip
and Latrobe Valley airshed. Top left- emissions of elemental carbon (kg cell h-1); top right 1-h ozone
concentrations (ppb); bottom-left concentrations of elemental carbon (g m-3); bottom- right
concentrations of SO (ppb). The model output is for 2 pm 11th March 2005. .......................................... 36
2
Figure 16. From top to bottom- observed and modelled temperature (C); SO (ppb), PM10 (g m-3),
2
ozone (ppb). The data are hourly average and the simulation period is 9-21st March 2005. The day
number corresponds to the simulation day- thus day 1 corresponds to 9th March. ................................. 37
Figure 17. The plot shows the Port Phillip and Latrobe Valley airsheds, and demonstrates how the
Melbourne emissions can be advected into the Latrobe Valley. The simulation is for 4 pm on 9th March
2005. The left hand plots show the combined SO (top) and sulfate (bottom) ground level
2
concentrations. The right plots show the modelled contribution to Loy Yang B at this time. Note SO
2
concentrations are in ppb; sulfate concentrations are in g m-3. .............................................................. 39
Figure 18. The plot shows the same as the previous plot only now on the 3 km spaced model grid which
is focussed on the Latrobe Valley. Note how the plumes downwind of the Loy Yang complex are now
better resolved. .......................................................................................................................................... 40
Figure 19. Top- 2nd highest daily 1-hour ozone concentration for the March 2005 simulation period.
Bottom left- scatter plot showing the contribution of the Loy Yang business-as-usual emissions to the
modelled ozone concentrations. Bottom right- scatter plot showing how the PCC contribution compares
to the BAU contribution. ............................................................................................................................ 43
Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
ii | Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant
Figure 20. Top- 2nd highest daily 1-hour SO concentration for the March 2005 simulation period for the
2
1-km modelling domain. Also shown is the contribution made by Loy Yang. Bottom - scatter plot
showing the contribution of the Loy Yang business-as-usual emissions to the modelled SO
2
concentrations. ........................................................................................................................................... 44
Figure 21. Top- 2nd highest daily 1-hour NO concentration for the March 2005 simulation period. Also
2
shown is the contribution made by Loy Yang. Bottom left- scatter plot showing the contribution of the
Loy Yang business-as-usual emissions to the modelled NO concentrations. Bottom right- scatter plot
2
showing how the PCC contribution compares to the BAU contribution.................................................... 45
Figure 22. Top- 6th highest 24-hour PM2.5 concentration for the March 2005 simulation period. Also
shown is the contribution made by Loy Yang. Bottom left- scatter plot showing the contribution of the
Loy Yang business-as-usual emissions to the modelled PM2.5 concentrations. Bottom right- scatter plot
showing how the PCC contribution compares to the BAU contribution.................................................... 46
Figure 23. Top- the modelled spatial distribution of maximum peak hourly ground level MEA
concentration for March 2005. Bottom- the frequency distribution of the same. .................................... 48
Figure 24. Top- peak 1-hour NH concentration for the March 2005 simulation period. Also shown is the
3
contribution made by Loy Yang. Bottom left- scatter plot showing the contribution of the Loy Yang
business-as-usual emissions to the modelled NH concentrations. Bottom right- scatter plot showing
3
how the PCC contribution compares to the BAU contribution. ................................................................. 49
Figure 25. Top- the modelled spatial distribution of maximum monthly average ground level nitrosamine
concentration for March 2005. Bottom- the frequency distribution of the same. .................................... 50
Figure 26. Top- the modelled spatial distribution of maximum monthly average ground level nitramine
concentration for March 2005. Bottom- the frequency distribution of the same. .................................... 51

Tables
Table 1. Initial amine, VOC and NOx mixing ratios for smog chamber experiments ................................... 7
Table 2. Chemical mechanisms used to simulate smog chamber experiments. .......................................... 8
Table 3. Summary of key product data for VOC, MEA, PZ and AMP experiments ....................................... 9
Table 4. Comparison of SAPRC (VOC only) and MCM (VOC only) O predictions against experimental
3
data ............................................................................................................................................................. 18
Table 5. Emissions (kg day-1) of key gaseous and particle species from the a) the EPAV Victorian air
emissions inventory; from Loy B. BAU- business as usual operations; PCC- assumed emissions after post
carbon capture. Note that NO emissions are given as NO + NO with NO converted to NO equivalent
x 2 2
mass. ........................................................................................................................................................... 34
Table 6. National Environment Protection Measure (NEPM) ambient air quality standards (AAQS)1 ...... 41

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List of Abbreviations
AAQS Ambient Air Quality Standards
AMP 2-Amino-2-methyl-1-propanol
BAU Business-as-usual
CI-MS Chemical Ionisation – Mass Spectrometry
CSIMEA - (MEA mechanism developed from CSIRO smog chamber experiments)
CTM Chemical Transport Model
DNPH 2,4-Dinitrophenylhydrazine
EI-MS Electron Ionisation – Mass Spectrometry
EPAV Environment Protection Authority Victoria
FTIR Fourier Transform Infrared Spectroscopy
GC/FID Gas Chromatography / Flame Ionisation Detector
HPLC High Performance Liquid Chromatography
MCM Master Chemical Mechanism
MEA 2-Aminoethanol (Monoethanolamine)
NEPM National Environment Protection Measures
NITC 1-NapthylIsothiocyanate
PPR Port Philip Region which encompasses Melbourne and Geelong
PZ Piperazine
SAPRC - (title of chemical mechanism; see Carter and Heo 2013)
SOA Secondary Organic Aerosol
TAPM The Air Pollution Model
TD-GCMS Thermal Desorption Gas Chromatography Mass Spectrometry
VOC Volatile Organic Compound

Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
iv | Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant
Acknowledgments
The authors wish to acknowledge financial assistance provided through Global Capture and Storage
Institute (Global CCS Institute). We also extend our acknowledgement for the financial assistance of the
CSIRO Energy Transformed Flagship.

Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant | v
Summary
The environmental impact of emissions from a PCC plant is one of the major challenges for the large scale
deployment of this technology. Issues related to the extent and environmental impacts of emissions of
amine solvents and their degradation products resulting from the future deployment of amine-based CO
2
capture technology to capture CO from fossil-fuelled power plant flue gases are needed for licensing and
2
operational permits.
In this report, an experimental and modelling study of the impact of ethanolamine (MEA) emissions from
the CSIRO Loy Yang pilot scale PCC plant was completed. A chemical transport modelling system was used
to simulate the likely impact of retrofitting a PCC installation to Loy Yang power station. A representative
month (March 2005) was selected on the basis of having many of the atmospheric process of relevance to
the chemical transformation of MEA and near-source plume strikes from the power station.
Due to the highly non linear complex chemical reactions that occur in the atmosphere between all existing
pollutants, the study of the photooxidation of amines was carried out using the CSIRO smog chamber.
These experiments were used to generate or modify existing chemical mechanisms describing the
atmospheric degradation of MEA in the atmosphere. The experiments completed in this study differed
from previously published results by the addition of other reactive volatile organic compounds (VOCs).
Smog chamber experiments of MEA in the presence of NOx and VOCs generated large amounts of aerosol
mass and moderate amount of ammonia through photochemical reactions. These experiments highlighted
a potential NOx-sink under certain conditions which was not identified from MEA experiments without
added VOCs. These conditions were not entirely well predicted by the current mechanisms, and further
work is required to assess whether these conditions are important in an ambient context, and if so to
improve upon the existing mechanisms.
One of the evaluated MEA chemical mechanisms was implemented into a chemical transport model to
simulate the impact of MEA emissions on the atmosphere surrounding the Loy Yang power station. The
most significant positive impact of the PCC modelling scenario is that SO emissions are significantly
2
reduced. The modelling suggested that Loy Yang contributed about 25% of the peak hourly SO within the
2
local region, and this was eliminated for the PCC scenario. Concentrations of PM2.5 were also reduced,
although the contribution of the power station emissions to ground level PM2.5 within the local region was
modelled to be small even for the BAU scenario.
Concentrations of ammonia are predicted to increase - both as a result of increased emissions, and from a
reduced conversion rate to ammonium in the presence of sulphate. However the ammonia concentrations
were small compared with the simulated concentrations resulting from surface-level sources such as
fertilised soils. The ground level concentrations of MEA and the reactants nitrosamine and nitramine were
also predicted to be small.
These results are likely to be a strong function of the source conditions. For example, primary pollutants
exhibit linear dependency with emission rate and exponential dependency with emission height. Increased
emissions from the PCC process released in a less buoyant plume, and/or from a lower release height has
the potential to incur a larger impact at ground level. A sensitivity study in which the emissions of MEA
were increased by an order of magnitude showed an approximately linear increase in the predicted MEA
concentrations at ground level. The secondary reactants such as nitrosamine and nitramine showed less
than linear increases, possibly as a result of the production rates being limited by other factors such as
hydroxyl radical availability and environmental conditions.
For the current case study it is apparent that the predicted concentrations of pollutants resulting from the
PCC emissions are lower than the limits in existing air quality guidelines.

Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
vi | Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant
Project Component 2:
Experimental and
modelling study of
the photo-
degradation of
monoethanolamine
Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant | 1
(MEA) in a mixed
VOC/NOx system

Assessing Atmospheric Emissions from Amine based CO2 PCC Process and their Impacts on the Environment – A Case Study
2 | Volume 2: Atmospheric chemistry of MEA and 3D air quality modelling of emissions from the Loy Yang PCC plant