Assessing atmospheric emissions from amine-based CO2
post-combustion capture processes and their impacts on the
environmen...
Dr Merched Azzi
Merched is a Chief Research Scientist at CSIRO Energy
Technology Australia and Research Leader for Emissio...
QUESTIONS
 We will collect questions during
the presentation.
 Your MC will pose these question
to the presenter after t...
Emissions from Amine-based PCC Plants- A Case
Study using Monoethanolamine - MEA
ENERGY TECHNOLOGY
Merched Azzi
Chief Rese...
Outline of the presentation
• Measurement of emissions
Development of appropriate techniques and procedures for collecting...
Flue gas
pretreatment
Flue Gas
CO2
SOx
NOx
PM
Trace Elements
Etc.
Gaps in knowledge around PCC plant
environmental perform...
Background
More degradation products are expected to form in the industrial operating
environment than in the laboratory e...
Lignite – Brown Coal
MEA based
No FGD/de-NOx
Operational since May 08
PCC Pilot Plant
AGL Loy Yang Power Station
Victoria,...
• Developed appropriate techniques to collect data from the absorber
• Developed procedures for analytical analysis for qu...
The CSIRO Smog Chamber Facility
• Smog chamber used to investigate the photo-
oxidation of amines and other organic
compou...
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 H...
[Melbourne- population 4M]
CSIRO atmospheric emissions meteorological chemical transport modelling system
Loy Yang A & B
1...
Global CCS Institute Melbourne Meeting June 2014| Merched Azzi
IEA 2010 OSLO Env. Impacts MEAProject Reviews
Secondary pro...
Compound
Solvent
liquor
Water
wash liquor
Inlet gas
stream
Absorber
outlet
Water wash
outlet
Monoethanolamine 28% w/v 4777...
The engineering control refers to the water
wash column at the top of absorber.
Nitrosomorpholine
Major findings
Emissions...
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
...
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
)
T...
-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 2n...
• A major degradation product of MEA.
• Peak ammonia concentrations near plant are,
for a short period of time, comparable...
Very low nitroso and nitramine (N-(2-hydroxyethyl)nitramide) predictions (picograms-pg m-3), despite
nitramine atmospheric...
Conclusions
What are the likely emissions?
 Without engineering control measures, MEA, ammonia, acetaldehyde, acetone,
fo...
Conclusions
What are the emissions formation mechanism and atmospheric dispersion?
 Smog chamber experiments have achieve...
Conclusions
How to control the emissions?
Proper engineering control measures are able to eliminate, minimise or control t...
Conclusions
A generalised Environmental Framework for assessing the emissions from amine-
based PCC plants has been develo...
ACKNOWLEDGEMENTS
We acknowledge financial assistance provided through Global
Capture and Storage Institute to accomplish t...
Thank you
CSIRO
Energy Flagship
Dr Merched Azzi
Chief Research Scientist
t +61 2 9490 5307
e merched.azzi@csiro.au
CSIRO -...
QUESTIONS / DISCUSSION
Please submit your questions in
English directly into the
GoToWebinar control panel.
The webinar wi...
Please submit any feedback to: webinar@globalccsinstitute.com
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Webinar: Assessing atmospheric emissions from amine-based CO2 post-combustion capture processes and their impacts on the environment

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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.

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Webinar: Assessing atmospheric emissions from amine-based CO2 post-combustion capture processes and their impacts on the environment

  1. 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. 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
  3. 3. QUESTIONS  We will collect questions during the presentation.  Your MC will pose these question to the presenter after the presentation.  Please submit your questions directly into the GoToWebinar control panel. The webinar will start shortly.
  4. 4. Emissions from Amine-based PCC Plants- A Case Study using Monoethanolamine - MEA ENERGY TECHNOLOGY Merched Azzi Chief Research Scientist July 2014
  5. 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. 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. 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. 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. 9. • Developed appropriate techniques to collect data from the absorber • Developed procedures for analytical analysis for quantifying pollutants Measurement of emissions
  10. 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. 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. 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. 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. 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. 15. The engineering control refers to the water wash column at the top of absorber. Nitrosomorpholine Major findings Emissions at absorber outlet
  16. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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
  27. 27. QUESTIONS / DISCUSSION Please submit your questions in English directly into the GoToWebinar control panel. The webinar will start shortly.
  28. 28. Please submit any feedback to: webinar@globalccsinstitute.com

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