This webinar presented the major findings of a CSIRO-led investigation into the potential air quality impacts of amine-based post-combustion carbon capture (PCC) technology. The study was commissioned by the Global Carbon Capture and Storage (CCS) Institute to expand knowledge on environmental impacts of the capture process, the study measures actual emissions as well providing a case study into air quality at the AGL Loy Lang PCC Plant in Victoria, Australia. The study aimed to address uncertainty about the types/quantities of pollutants released during PCC plant operations and what their acceptable emissions levels were. Understanding this would allow industry and regulators to develop appropriate health and safety practices around PCC plants. The research was based on data collected at CSIRO’s PCC pilot plant at the AGL Loy Yang brown coal-fired power plant in Victoria, Australia and from atmospheric degradation experiments in CSIRO’s smog chamber in New South Wales, Australia. Dr Merched Azzi, Chief Research Scientist from CSIRO Energy Technology presentied this webinar.

1. Assessing atmospheric emissions from amine-based CO2
post-combustion capture processes and their impacts on the
environment
Webinar – 09 July 2014, 1700 AEST

2. Dr Merched Azzi
Merched is a Chief Research Scientist at CSIRO Energy
Technology Australia and Research Leader for Emissions
from Energy Cycles. He has over 20 years experience in
industrial and government research organisations with a
broad base of technical skills in chemical engineering,
atmospheric science, and air quality modelling.
He conducted numerous state-of-the-art, high impact and
world class scientific research relating to the fate of
emissions from current and emerging energy sources. His
research has provided the scientific knowledge required by
industry and regulators to work together towards
implementing the appropriate policies for local, regional
and global pollution reductions.
Chief Research Scientist, CSIRO Energy Technology-Australia

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4. Emissions from Amine-based PCC Plants- A Case
Study using Monoethanolamine - MEA
ENERGY TECHNOLOGY
Merched Azzi
Chief Research Scientist
July 2014

5. Outline of the presentation
• Measurement of emissions
Development of appropriate techniques and procedures for collecting
emission data from PCC plants
• Photochemical mechanisms
Development of an appropriate chemical mechanism describing the
atmospheric degradation of the selected solvent
• Emission dispersion
Predicted the ground level concentrations and environmental fates of major
pollutants
• Major findings
What, why, and how?
Reports: http://www.globalccsinstitute.com/publications/assessing-atmospheric-emissions-amine-
based-co2-post-combustion-capture-processes-and-their-impacts-environment-case-study

6. Flue gas
pretreatment
Flue Gas
CO2
SOx
NOx
PM
Trace Elements
Etc.
Gaps in knowledge around PCC plant
environmental performance
Purpose of the study

7. Background
More degradation products are expected to form in the industrial operating
environment than in the laboratory environment. Therefore one needs more pilot
plant campaigns to generate the real time information.
Bearing in mind that “Prevention is the Best Medicine”, we developed a strategy that
addresses the following aspects:
• Develop appropriate techniques and procedures to collect data from PCC
plants
• Chemical mechanism to describe atmospheric degradation of selected solvents
• Predict ground level concentrations of major pollutants
• Develop a generalised framework to assess emissions from PCC plants
By combining the results obtained during the current project and those
obtained by a parallel project funded by ANLEC, the results have allowed us to
developed a generalised framework to assess the fate of emission from PCC
plants .

8. Lignite – Brown Coal
MEA based
No FGD/de-NOx
Operational since May 08
PCC Pilot Plant
AGL Loy Yang Power Station
Victoria, Australia
Focus: Benchmarking of solvents
Low investment cost
Measurement of emissions

9. • Developed appropriate techniques to collect data from the absorber
• Developed procedures for analytical analysis for quantifying pollutants
Measurement of emissions

10. The CSIRO Smog Chamber Facility
• Smog chamber used to investigate the photo-
oxidation of amines and other organic
compounds
A rigid rectangular chamber: 1.98m x 3.71m x 2.46m
Volume: 18.1 m3 Surface area: 42.7 m2 Surface to volume ration:
2.36 m-1.
• Results used to develop and validate chemical
mechanism which describe the most important
features of degradation
• Different mixtures of amine, NOx and VOCs were
used to carry out experiments
A mechanism describing the degradation
of MEA has been developed, validated
and tested using emissions from the
LYPCC plant
Photochemical mechanisms

11. MEA Chemical Mechanism
Rate Reaction Products Reference (rate)
7.73 x 10-11 (T/295)-0.79 MEA + OH 0.40 x MEAC2PER
0.05 x HNCH2CH2OH
0.55 x HNCHCH2OH + HO2
Onel et al. (2012)
1.75 x 10-12 MEA + NO3 MEANO3 This work, fitted
2.70 x 10-12 e(360/T) MEAC2PER + NO MEAC2OXY + NO2 MCM protocol
1.52 x 10-13 e(1300/T) MEAC2PER + HO2 MEAC2HPE MCM protocol
1.0 x 106 MEAC2OXY H2NCHO + HCHO + HO2 MCM protocol
J<41> MEAC2HPE H2NCOCH2OH + OH MCM protocol
1.90 x 10-12 e(190/T) MEAC2HPE + OH MEAC2PER MCM protocol
1.70 x 10-10 MEAC2HPE + OH H2NCOCH2OH + OH SAR
J<22> H2NCOCH2OH HNCO + HCHO + HO2 + HO2 MCM protocol
6.59 x 10-12 H2NCOCH2OH + OH H2NGLYOX + HO2 SAR
1.01 x 10-18 HNCHCH2OH + O2 HNCHCH2OH + HO2 This work, fitted
8.53 x 10-14 HNCHCH2OH + NO MEANITROSO Lazarou et al. (1994)
3.95 x 10-13 HNCHCH2OH + NO2 0.82 x MEANITRA
0.18 x HNCHCH2OH + HONO
Lindley et al. (1979)
relative to above
J<4> x 0.33 MEANITROSO HNCHCH2OH + NO Nielsen et al. (2010)
1.00 x 10-17 MEANITROSO + O2 HNCHCH2OH + HO2 + NO Nielsen et al. (2011a)
6.52 x 10-12 MEANITRA + OH HNCHCH2OH + NO2 Nielsen et al. (2012b)
1.67 x 10-11 H2NGLYOX + OH HNCO + CO + HO2 SAR
5.60 x 10-12 e(-1860/T) H2NGLYOX + NO3 HNO3 + HNCO + HO2 + CO MCM protocol
J<34> H2NGLYOX HNCO + HO2 + HO2 + CO MCM protocol
4.00 x 10-12 H2NCHO + OH HNCO + HO2 Barnes et al. (2010)
1.40 x 10-12 e(-1860/T) H2NCHO + NO3 HNCO + HNO3 + HO2 MCM protocol
6.00 x 10-12 HNCHCH2OH +
HNCHCH2OH
SECIMINE + NH3 This work, estimated
5.00 x 10-10 HNCHCH2OH + OH H2NCOCH2OH + HO2 This work, estimated
1.00 x 106 HNCHCH2OH + H2O NH3 + HOCH2CHO This work, set
deliberately fast.
1.00 x 10-18 HNCO + H2O NH3 This work, estimated
1.00 x 10-11 OXAZOL* + OH 0.80 x LAMINYL
0.20 x NRIMINE + HO2
This work, estimated
1.00 x 10-13 OXAZOL* + NO3 0.80 x LAMINYL
0.20 x NRIMINE + HO2
1.00 x HNO3
This work, estimated
3.18 x 10-13 LAMINYL + NO2 0.625 x LNITRA
0.375 x NRIMINE
0.375 x HONO
Nielsen et al. (2012a)
for morpholine
(cyclic oxy. amine)
1.81 x 10-13 LAMINYL + NO LNITROSO Nielsen et al. (2012a)
3.82 x 10-19 LAMINYL + O2 NRIMINE + HO2 Nielsen et al. (2012a)
J<4> x 0.31 LNITROSO LAMINYL + NO Nielsen et al. (2012a)
3.50 x 10-12 LNITRA + OH NRIMINE + HO2 + NO2 This work, estimated
1.80 x 10-17 MEA + HCHO OXAZOL This work
1.20 x 10-16 MEA + HOCH2CHO GLYCOLINT This work, estimated
5.00 x 10-14 MEA + GLYCOLINT MEAGLYCOL This work, estimated
4.00 x 10-11 MEA + HNO3 MEANTR (AEROSOL) Carter (2008)
1.40 X 10-12 MEAC2PER + RO2 0.60 x MEAC2OXY
0.40 x H2NCOCH2OH
MCM Protocol
• MEA mechanism developed
• Nitrosamine reactions limited the
concentration of nitrosamines to
negligible amounts
• Gas phase ammonia production
included

12. [Melbourne- population 4M]
CSIRO atmospheric emissions meteorological chemical transport modelling system
Loy Yang A & B
1,000 MW
7 Mt/yr CO2
Stack height: 255 m
Atmospheric dispersion

13. Global CCS Institute Melbourne Meeting June 2014| Merched Azzi
IEA 2010 OSLO Env. Impacts MEAProject Reviews
Secondary products:
ozone, aerosols,
other air toxics
Smog Chamber
Chemical transformation
Chemical reactions
Impacts
Human health
Ecosystem health
Primary emissions
e.g. Amines, VOCs, NOx,
SOx, PM,
greenhouse gases, other air
toxics
Dry and wet
deposition
Meteorology
Transport/diffusion
Predict how GLCs of
pollutants will respond to
changes in emissions?
Industry/
power plant Transport Biogenics
Emission Inventory
Windfields/dispersion
Chemical mechanism
AQMs
2-D Langrangian Model
3-D (CTM)
Atmospheric Fate of major pollutants

14. Compound
Solvent
liquor
Water
wash liquor
Inlet gas
stream
Absorber
outlet
Water wash
outlet
Monoethanolamine 28% w/v 4777 ND 312 ND
Ammonia 299 1389 ND 204 250
Methylamine ND ND ND 1.3 0.068
Ethylamine ND ND ND 0.12 0.009
Dimethylamine ND ND ND 0.026 0.003
Formaldehyde ND 2.2 ND 0.1 0.08
Acetaldehyde 0.4 0.5 ND 0.8 1.1
Nitrosodimethylamine ND 1.1 µg/L ND ND ND
Nitrosomorpholine 16 µg/L 6.4 µg/L ND 0.32 µg/Nm3
0.04 µg/Nm3
Nitrosodiethanolamine 2.8 mg/L ND ND ND ND
Concentration
mg/L mg/Nm
3
Major findings
Emissions at absorber outlet

15. The engineering control refers to the water
wash column at the top of absorber.
Nitrosomorpholine
Major findings
Emissions at absorber outlet

16. 0 50 100 150 200
0
20
40
60
80
100
120
140
160
0
100
200
300
400
500
NH3
NH3
,O3
,NOx
MixingRatio(ppb)
Time (min)
O3
~NO2
NO
~NOx
MEA
E514: MEA 490 ppb, NOx 51 ppb
MEAMixingRatio(ppb)
NH3
O3
 MEA
NO
NOx
Major findings
Smog chamber results VOC/NOx = 20

17. 0 40 80 120 160 200 240
0.0
2.0x10
4
4.0x10
4
6.0x10
4
8.0x10
4
1.0x10
5
1.2x10
5
0
200
400
600
800
NumberConc.(N/cm
3
)
Time (min)
E514: MEA 490 ppb, NOx 51 ppb
TotalMassConc.(g/m
3
)
Major findings
Secondary Organic Aerosol(SOA) formation (VOC/NOx = 20)

18. -1.5
-1.0
-0.5
0.0
0.5
1.0
0 20 40 60 80 100 120
BAUcontributionto1-hO3
1-h O3 from allsources (ppb)
BAUcontribution to 2nd highest 1-h O3
-1.5
-1.0
-0.5
0.0
0.5
1.0
-1.5 -1 -0.5 0 0.5 1 1.5
PCCcontributionto1-hO3(ppb)
BAU contribution to 1-h O3 (ppb)
PCC vs BAUcontributionto2nd highest 1-hO3
Ozone
Small losses
due to titration
in NO plume
BAU contributes < 1%
to the PM2.5 goal.
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
-0.1 0 0.1 0.2 0.3 0.4
PCCcontribution(gm-3)
BAUcontribution(gm-3)
PCC vs BAU - 1 km domain
PM2.5
Major findings
Impact on Criteria Pollutants

19. • A major degradation product of MEA.
• Peak ammonia concentrations near plant are,
for a short period of time, comparable to
concentrations resulting from soil fertilisation
in the north of Gibbsland
0
20
40
60
0 25 50 75
BAUcontributiontopeak1-hNH3
Peak1-h NH3 from all sources (ppb)
PCC contribution to highest 1-h NH3
Major findings
Ammonia Concentrations

20. Very low nitroso and nitramine (N-(2-hydroxyethyl)nitramide) predictions (picograms-pg m-3), despite
nitramine atmospheric stability
Major findings
Impact on Criteria Pollutants

21. Conclusions
What are the likely emissions?
 Without engineering control measures, MEA, ammonia, acetaldehyde, acetone,
formaldehyde are likely to be emitted from the carbon capture process.
 Levels of suspected carcinogenic nitrosamines and nitramines released
during the Loy Yang PCC operations were negligible and extremely unlikely
to impact on human health or exceed current air quality standards.
 Flue gases from power plants fitted with post combustion capture are
expected to be much cleaner with lower levels of pollution than plants
without the technology, despite the release of substances derived from the
amine plant. The process of removing CO₂ from the flue gases also greatly
reduces the other common pollutants.

22. Conclusions
What are the emissions formation mechanism and atmospheric dispersion?
 Smog chamber experiments have achieved excellent understandings of the mechanisms
for the formation of different compounds in the capture process.
 Atmospheric dispersion can also be determined under different weather
conditions and air quality.

23. Conclusions
How to control the emissions?
Proper engineering control measures are able to eliminate, minimise or control the
emission to ensure compliance with the current standards/guideline of air quality.
With adequate engineering measures in place, the quantities of emission may be kept far
below the current limits specified by various air quality standards/guidelines and may
have little/no impact on the environment.

24. Conclusions
A generalised Environmental Framework for assessing the emissions from amine-
based PCC plants has been developed, and the framework can be applied to any
other amine-PCC plant includes:
• Developed, validated and implemented best practises to collect data from the plant
including (Stack sampling methods, sampling materials, methods to conserve target
compounds etc.)
• Developed and validated analytical procedures to isolate and quantify major
components and trace products in the process (wide range of analytical techniques for
identification and quantifying solvents, alkylamines, ammonia, amides, aldehydes,
nitrosamines, anions and metal species.
• Establish atmospheric chemical reactions for reactive pollutants
• Update chemical transport models to include the atmospheric chemistry of major
pollutants
• Determine ground level concentrations of pollutants over a selected airshed
• Local and regional air quality assessment for the deployment of MEA-based PCC can be
carried out using the developed chemical mechanism.

25. ACKNOWLEDGEMENTS
We acknowledge financial assistance provided through Global
Capture and Storage Institute to accomplish this work. We also
extend our acknowledgement for accessing data obtained from a
project funded by the Australian National Low Emissions Coal
Research and Development (ANLEC R&D).

26. Thank you
CSIRO
Energy Flagship
Dr Merched Azzi
Chief Research Scientist
t +61 2 9490 5307
e merched.azzi@csiro.au
CSIRO - ENERGY FLAGSHIP

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