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

158 Pages·2014·3.09 MB·English

ENERGY FLAGSHIP

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

Volume 1
Measurement of emissions from a monoethanolamine-based
post-combustion CO capture pilot plant
2

Final Report
Merched Azzi, Anne Tibbett, Brendan Halliburton, Adrian Element, Yuli Artanto, Erik Meuleman, Paul
Feron
May 2014
Global Carbon Capture and Storage Institute (Global CCS Institute)
Energy Flagship
Citation
Azzi M., Tibbett A., Halliburton B., Element A., Artanto Y., Meuleman E., Feron P. (2014)
Assessing Atmospheric Emissions from Amine-based CO Post-combustion Capture Processes and their
2
Impacts on the Environment – A Case Study. Volume 1: Measurement of emissions from a
monoethanolamine-based post-combustion CO capture pilot plant. CSIRO, Australia.
2
Copyright and disclaimer
© Global Carbon Capture and Storage Institute Limited 2014 Melbourne. To the extent permitted by law,
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Contents
Glossary ......................................................................................................................................................... v
Acknowledgments ....................................................................................................................................... vii
Project Overview ........................................................................................................................................ viii
Executive Summary ...................................................................................................................................... ix
Background to Carbon Capture and Storage and its Environmental Implications ....................................... xi
Project Component 1: 1
Measurement of emissions from a monoethanolamine-based post-combustion capture pilot plant 1
1 Introduction .................................................................................................................................... 2
2 The Post-Combustion CO Capture Pilot Plant ................................................................................ 3
2
2.1 Pilot plant description ........................................................................................................... 3
2.2 Pilot plant operation ............................................................................................................. 6
3 Sampling Points ............................................................................................................................. 16
3.1 Criteria for representative sampling ................................................................................... 16
3.2 Sampling requirements for the Loy Yang Pilot Plant .......................................................... 16
3.3 Installation of the sampling plane at the water wash exit ................................................. 17
3.4 Installation of the sampling plane at the absorber exit ...................................................... 18
3.5 Gas flow in post-combustion capture pilot plant – computational fluid dynamic
analyses ......................................................................................................................................... 18
3.6 Solvent distributor design study ......................................................................................... 19
3.7 New solvent distributor design ........................................................................................... 20
4 Sampling Methodology ................................................................................................................. 22
4.1 Sampling port interfacing ................................................................................................... 22
4.2 Stack sampling apparatus ................................................................................................... 26
4.3 Validation of sampling methods ......................................................................................... 31
4.4 Sampling review and conclusions ....................................................................................... 42
5 Analytical Methodologies ............................................................................................................. 43
5.1 Monoethanolamine and diethanolamine ........................................................................... 45
5.2 Ammonia ............................................................................................................................. 49
5.3 Alkylamines ......................................................................................................................... 52
5.4 Amides ................................................................................................................................ 56
5.5 Nitrosamines ....................................................................................................................... 56
5.6 Carbonyls (aldehydes and ketones) .................................................................................... 61
5.7 Anions ................................................................................................................................. 62
5.8 Metals ................................................................................................................................. 63
5.9 Summary performance of the analytical methods for PCC process assessment ............... 64
5.10 Analytical conclusions and recommendations ................................................................... 68
6 Emissions Results .......................................................................................................................... 69
7 Concluding Remarks ...................................................................................................................... 73
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References .................................................................................................................................................. 74
Appendix A Water Wash Simulation using ProTreat simulator ............................................................. 76
Appendix B Analytical Technical Reports ............................................................................................... 79

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Figures
Figure 1. Process flow diagram of the CSIRO post-combustion capture pilot plant operating without
process gas pre-treatment ........................................................................................................................... 3
Figure 2. Process parameters affecting CO recovery and reboiler heat duty as a function of operating
2
time ............................................................................................................................................................... 7
Figure 3. Monoethanolamine loss distribution for 0–300 and 300–800 hours ......................................... 10
Figure 4. CO balance, CO concentrations (gas phase) and monoethanolamine (MEA) concentration
2 2
(liquid phase) around the plant .................................................................................................................. 11
Figure 5. Gas and liquid sampling locations in the CSIRO post-combustion capture pilot plant ............... 12
Figure 6. Typical CO balance during the CSIRO post-combustion capture pilot plant operation ............. 13
2
Figure 7. Heat-stable salt (HSS) concentration in combined campaigns: Tarong and Loy Yang pilot
plant ............................................................................................................................................................ 15
Figure 8. Pressure drop and flow rates during the experimental campaign at Loy Yang pilot plant ......... 15
Figure 9. Identified sample points at the Loy Yang post-combustion capture pilot plant. A, process gas
inlet after initial cooling and condensation removal; B, Absorber Column 2 after absorption before the
water-wash section; C, process gas return line .......................................................................................... 16
Figure 10. Sampling port at the outlet of the Loy Yang pilot plant, identified as point ‘C’. ....................... 17
Figure 11. Solvent distributor in Column 1 ................................................................................................. 18
Figure 12. Computational fluid dynamic modelling results at 158 m3/hr gas flow rate of the existing
solvent distributor (left), and the effect of grip-type flow straighteners: long (top right) and short
(bottom left) ............................................................................................................................................... 19
Figure 13. Solvent distributor design study (left) and computational fluid dynamic modelling results at
158 m3/hr gas flow rate (right) ................................................................................................................... 20
Figure 14. New solvent distributor design (left) and computational fluid dynamic modelling results at
158 m3/hr gas flow rate (right) ................................................................................................................... 20
Figure 15. Standard showerhead type distributor (left) and flow straightener and new custom-made
distributor (right) after installation ............................................................................................................ 21
Figure 16. Old demister being replaced with a new improved demister ................................................... 21
Figure 17. Diagrammatic representation of the sampling plug installed at each sampling port
(perspective view) ...................................................................................................................................... 22
Figure 18. Diagrammatic representation of the sampling plug installed at each sampling port (top, plan
view and bottom, elevation view) .............................................................................................................. 23
Figure 19. Source sampling apparatus installed into the outlet sampling port at Loy Yang pilot plant,
showing glass impinger train ...................................................................................................................... 24
Figure 20. Sampling port at the outlet of the Loy Yang pilot plant. The heated probe, the additional
curved section of heated sampling probe and ball valve can also be seen ............................................... 24
Figure 21. Sampling port located at the inlet to the water-wash section at the Loy Yang pilot plant....... 25
Figure 22. APEX Instruments (North Carolina USA) model XC-572 source sampling system .................... 26
Figure 23. Diagram of the impinger assembly and heated probe used during Loy Yang pilot plant
sampling measurements ............................................................................................................................ 27
Figure 24. Diagram of the impinger assembly with inserted condenser and heated probe used during Loy
Yang pilot plant sampling measurements .................................................................................................. 28
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Figure 25. Mass captured for each impinger relative to impinger placement in the sampling train, spiked
sample ........................................................................................................................................................ 36
Figure 26. Mass captured for each impinger relative to impinger placement in the sampling train, non-
spiked sample ............................................................................................................................................. 37
Figure 27. Mass captured for each impinger relative to impinger placement in the sampling train for the
modified USEPA Methods 0011 (organic phase), non-spike sample ......................................................... 41

Tables
Table 1. Post-combustion capture pilot plant design information .............................................................. 5
Table 2. Typical process gas properties from AGL Loy Yang Power plant received by the CSIRO Loy Yang
pilot plant ..................................................................................................................................................... 6
Table 3. Monoethanolamine (MEA) loss determination ............................................................................ 10
Table 4. Overview of process conditions during the campaign at CSIRO Loy Yang pilot plant .................. 14
Table 5. Analyte contact surfaces during sampling .................................................................................... 26
Table 6. Sampling methods followed during measurements at Loy Yang pilot plant ................................ 28
Table 7. Collection efficiencies and recoveries of USEPA Method 0011 and USEPA 8315A ...................... 29
Table 8. Treatments used to stabilise compounds within the impinger train ........................................... 31
Table 9. Sample background, transport and storage stability and impinger collection efficiency
assessment ................................................................................................................................................. 32
Table 10. Carbonyl impinger results from the first sampling campaign .................................................... 34
Table 11. Dependence of the number of impingers and collection efficiency .......................................... 35
Table 12. Validation of USEPA Method 0011 ............................................................................................. 38
Table 13. Validation of 2,4-dinitrophenylhydrazine (DNPH)/organic phase sample collection ................. 40
Table 14. Method detection limits (MDLs) for ion chromatography methodology for monoethanolamine
(MEA) and diethanolamine (DELA) in process liquids, and as the equivalent gas-phase concentration
under nominal sampling parameters ......................................................................................................... 47
Table 15. Analytical methodologies and sensitivity limits for priority compounds in post-combustion
capture process solutions from Phase 2 assessment ................................................................................ 65
Table 16. Analytical methodologies implemented and their applicability to post-combustion capture
process assessment of priority compounds ............................................................................................... 67
Table 17. Concentrations of priority compounds in process liquors and in process gas streams ............. 69

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Glossary
Analyte Substance or chemical constituent that is of interest in an analytical procedure
Alkylamines Decomposition products from amine-based post-combustion capture operations
Methylamine (MA)
Ethylamine (EA)
Dimethylamine (DMA)
Diethylamine (DEA)
Computational fluid dynamics (CFD) Branch of fluid mechanics that uses numerical methods and algorithms to solve and
analyse problems involving fluid flows
Counter flow When one fluid (gas) is moving in the opposite direction to a second fluid (liquid)
Diethanolamine (DELA) Impurity or decomposition product from amine-based post-combustion capture
operations
Detection limit (DL) or method A statistically derived measure of sensitivity of a specific aspect of the method, or as an
detection limit (MDL) equivalent for combined aspects of the methodology
2,4-dinitrophenylhydrazine (DNPH) Agent used to derivatise carbonyl compounds, specifically aldehydes and ketones
Electrostatic particle precipitator Particle removal device that uses high voltage to separate particles from a gas stream
(ESP)
Flue gas stream Exhaust gas stream within an industrial process that exits to the atmosphere
Gas-phase chromatography with Technique that combines the physical separation capabilities of gas phase
tandem mass spectrometry chromatography with the mass analysis capabilities of mass spectrometry (GCMS).
(GCMSMS) MSMS uses two stages of mass spectrometry to provide additional mass analysis data
Heat exchanger Device used to transfer heat from one fluid stream to another
Heat-stable salts A range of stable salts produced in a post-combustion capture solvent during operation
Ion chromatography (IC) Technique that allows the separation of ions and polar molecules based on their charge
Impinger Vessel that collects analytes during stack sampling operations
Isokinetic sampling The process of collecting aerosol in a moving stream that moves at the same velocity in
the sampling nozzle as elsewhere in the stream
Knock-out drum Separator for separating liquid and solid phases from a gas stream
Liquid-phase chromatography with Technique that combines the physical separation capabilities of liquid chromatography
tandem mass spectrometry with the mass analysis capabilities of mass spectrometry (LCMS). MSMS uses two stages
(LCMSMS) of mass spectrometry to provide additional mass analyses data
Monoethanolamine (MEA) The most commonly used solvent for CO post-combustion capture
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MEA 600+ Solvent used in this study, aged for 600 hours at the CSIRO Tarong pilot plant
Multiple reaction monitoring (MRM) Mass spectrometry (MS) technique that delivers a characteristic fragment ion that can
be monitored and quantified in the midst of a complicated matrix
N-Nitrosodiethanolamine (NDELA) Product formed from the nitrosation of diethanolamine
N-Nitrosodiethylamine (NDEA) Product formed from the nitrosation of diethylamine
N-Nitrosodimethylamine (NDMA) Product formed from the nitrosation of dimethylamine
N-Nitrosomorpholine Product formed from the nitrosation of morpholine
Nm³ Gas volume in cubic metres at 20 °C and 1 atmosphere pressure
Post-combustion capture (PCC) Removal of CO from power station flue gas prior to its compression, transportation
2
and storage in suitable geological formations, as part of carbon capture and storage
(CCS)
Process gas stream Any gas stream within an industrial process: in the context of this report, this is the
post-combustion capture plant
Reclaimer Section of a post-combustion capture plant where heat-stable salts are removed from a
solvent
Relative percent difference (RPD) The difference between numbers based as a percent of their average
An indicator of precision from duplicate measurements
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Relative Standard Deviation (RSD, %) The standard deviation of replicate measurements as a percent of their mean
An indicator of precision from replicate measurements
‘Spike’ (in the context of target An accurately known addition of target added to a solution, such as an impinger liquid
analytes) or a solution for analysis, to measure recoveries and validate sample collection and
analytical methods
Sampling Extracting target compounds from a fluid system
Sampling point The position in a process gas stream where sampling operations are undertaken
Sampling plane The fluid plane over which sampling operations are undertaken within a process fluid
pipe or duct. Usually undertaken orthogonal to the fluid flow
Solvent (in the process context) The liquid phase used to absorb CO in a post-combustion capture plant
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Stack Chimney and flue ductwork transporting exhaust gases from a combustion furnace
Stripper Section of a post-combustion capture plant where CO is released from the solvent
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Titration The process of determining the concentration of a substance in solution by adding to it
a standard reagent of known concentration in carefully measured amounts until a
reaction of definite and known proportion is completed. The equivalence, or end point,
is often determined by a colour change or by electrical measurement, and then
calculating the unknown concentration
Wet scrubbing The process of removing a target gas or gases from a gas stream using a liquid phase

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Acknowledgments
The authors wish to acknowledge financial assistance provided through Global Capture and Storage
Institute. We also extend our acknowledgement for the financial assistance of the CSIRO Energy
Transformed Flagship.
We would like to thank James Jansen, Owen Farrell, Aaron Cottrell, Hoda Javanmard and Scott Morgan
from CSIRO for their technical efforts.
We would like to extend our thanks to Rama Nimmagadda from Advanced Analytical Australia (AAA), and
to Phil Bridgen from AsureQuality NZ for their expertise in securing high-level analytical performance in the
methods developed for this project. Mark Lewin from AAA, Vince Verheyen and Alicia Reynolds from
Monash University and the personnel at SGS Leeder Consulting are also thanked for their considerable
attention to the analytical effort.

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Project Overview
The Global Carbon Capture and Storage (CCS) Institute commissioned CSIRO to investigate atmospheric
emissions from amine-based CO post-combustion capture (PCC) processes, and evaluate the potential
2
environmental impact of these emissions using a case study approach. The outcome of this study is the
assessment of these environmental and human health impacts within the context of the commercialisation
and widespread deployment of amine-based PCC.
Working towards improving PCC technology and accelerating the global deployment of commercial-scale
CCS projects, the Global CCS Institute brings together projects, policy makers and researchers to underpin
major challenges related to CCS deployment. It uses lessons learnt from CCS projects around the world to
provide information to a broad audience and improve our understanding of the technical, economic,
financial, commercial and engagement issues faced by CCS.
The research comprised three separate but interlinking components:
1. Quantifying emissions of an amine-based PCC process, which is the focus of this report. The
CSIRO PCC pilot plant located at AGL Loy Yang coal-fired power station was selected as the test
facility, using the most common or benchmark amine, monoethanolamine (MEA).
2. Evaluating photochemical mechanisms associated with selected amine systems, using the
CSIRO Smog Chamber facility.
3. Assessing the risk associated with future deployment of amine-based PCC plants, using air
quality modelling to predict the atmospheric fate and environmental risk of selected PCC-
generated compounds. The modelling experiments included measured PCC process data, as well as
smog chamber mechanistic and kinetic results.
The findings from Component 1 are presented in Volume 1 of the project report, The measurement of
emissions from a monoethanolamine-based post-combustion capture pilot plant, and are the subject of this
document. Components 2 and 3 are presented in Volume 2 of the report, Atmospheric chemistry of
monoethanolamine and 3D air quality modelling of emissions from the Loy Yang post-combustion capture
plant.
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