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LABORELEC © LABORELEC ©
On- and off-line ethanolamine and ammonia emission monitoring
in PCCC
Jan Mertens, Dominique Desagher, Marie-Laure Thielens, Han Huynh , Helene Lepaumier, LABORELEC, Linkebeek, Belgium
Purvil Khakaria, Earl Goetheer,, TNO, Delft, The Netherlands
2
Materials and methods used
On-line measurement of organics (MEA, aldehydes,…) and inorganics (NH3, CO2, H20, …) at ppm level FTIR
On-line measurement of PM/aerosol size distribution & concentration between 6 nm & 10 µm ELPI+
Off-line measurement of the gas phase: mostly used for NH3, MEA, aldehydes, nitrosamines Manual sampling
3
Materials and methods used
On-line measurement of organics (MEA, aldehydes,…) and inorganics (NH3, CO2, H20, …) at ppm level FTIR
4
High MEA emissions have been observed during different pilot plant campaigns at different locations
High emissions measured also in US: Project NCCC in Alabama http://www.netl.doe.gov/publications/proceedings/12/co2capture/presentations/2-Tuesday/T%20Carter-NCCC-Post-combustion.pdf
From 0.25 to 1.6 g/Nm³
High MEA emissions measured using FTIR at different pilots in EU: Mertens, J., M. L. Thielens, J. Knudsen and J. Andersen, 2012. On-line monitoring and controlling emissions in amine post combustion carbon capture: a field test. International Journal of Greenhouse Gas Control, 6, 2-11 Mertens, J., H. Lepaumier, D. Desagher and M.L. Thielens, 2013. Understanding Ethanolamine (MEA) and ammonia emissions from amine based post combustion carbon capture: lessons learned from field tests. International Journal of Greenhouse Gas Control, 13, 72-77
5
High MEA emissions are linked to the presence of very fine aerosols and particulate matter in the power plant flue gases
Eg. Effect of lead change had temperarue effect on MEA emissions linked to changes in incoming SO3 aerosols and PM )
Change in Power plant load (see O2 concentration change) : sharp increase in MEA emissions Can be linked to: increase in PM/SO3 aerosol emissions from power plant formation of MEA aerosols inside absorber Confirmed by other studies eg.: Khakharia P., L. Brachert , J.Mertens , A. Huizinga, B. Schallert , K. Schaber , T. J.H. Vlugt and Earl Goetheer, 2013. Investigation of aerosol based emission of MEA due to sulphuric acid aerosol and soot in a Post Combustion CO2 Capture process. International Journal of Greenhouse Gas Control, accepted Kamijo, T., 2011. Amine Emission Control Technology of KM CDR ProcessTM, Presentation at the EPRI meeting: ‘Amines for post combustion Capture, 16th August 2011. Kolderup, H., E. da Silva, T. Mejdell, A. Tobiesen, G. Haugen, K. A. Hoff, K. Josefsen, T. Strøm; O. Furuseth, K. F. Hanssen, H.Wirsching, T. Myhrvold and K. Johnsen , 2011. Emission Reducing Technologies. Report H&ETQP Amine6 for Gassnova NF, Norway Knudsen; J. and O. Bade; 2012: Emission Reduction Technologies; CLIMIT Workshop 5-6 December 2011, Oslo, Norway. Available at www.akercleancarbon.com
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Water wash not successful in removing all MEA emissions indicates the presence of MEA in the form of aerosols
Water wash has no effect on NH3 Water wash only reduces MEA emissions to around 50 %: not all MEA is gaseous
MEA aerosols
0
20
40
60
80
100
NH
3 an
d M
EA
(%
)
0
20
40
60
80
100
Wat
er c
on
ten
t (v
ol %
)
NH3
MEAWater
IN
OUT
7
Materials and methods used
On-line measurement of organics (MEA, aldehydes,…) and inorganics (NH3, CO2, H20, …) at ppm level FTIR
On-line measurement of PM/aerosol size distribution & concentration between 6 nm & 10 µm ELPI+
8
Characterisation of the amount and size of aerosols using ELPI+
ELPI = Electrical Low Pressure Impactor
Real-time measurement of particle size distribution and concentration between 6 nm to 10 µm
Working principle: 1. Particle charging 2. Size classification in a cascade impactor (15 size classes) 3. Electrical detection with sensitive electrometers
D50%
[µm]
15 10
14 6.8
13 4.4
12 2.5
11 1.6
10 1.0
9 0.64
8 0.40
7 0.26
6 0.17
5 0.108
4 0.060
3 0.030
2 0.017
1 0.006
Stage
9
18:52:07 19:08:47 19:25:27 19:42:07 19:58:47
Nu
mb
er (
cm-3
)
0.01 µm
0.02 µm
0.04 µm
0.07 µm
0.12 µm
0.20 µm
0.32 µm
0.48 µm
0.76 µm
1.23 µm
1.95 µm
3.08 µm
5.15 µm
8.11 µmTOTAL
Different types of flue gas filters and their effect on PM/aerosol size and numbers are being evaluated
Clear correlation between the number of PM/aerosols entering the absorber and the MEA emissions
FILTER OFF FILTER ONFILTER OFF
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Correlation between ELPI+ (PM/aerosol number concentration) and FTIR measurements (MEA) allows a better understanding of the aerosol issue
Type of flue gas High MEA emission measured
Flue gas 1 Yes
Flue gas 2 Yes
Flue gas 2 filtered No
Flue gas 3 No
0.01 0.1 1 10Size (µm)
Nu
mb
er c
on
cen
trat
ion
(cm
-3)
Flue gas 1Flue gas 2Flue gas 2 (filtered)Flue gas 3Ambient air
11
Aerosol total number only slightly affected but aerosol size increases significantly as they move through the absorber
0.01 0.1 1 10Size (µm)
Nu
mb
er c
on
cen
trat
ion
(cm
-3)
in front of absorberbehind absorber
Aerosols mainly grow inside the absorber through the take-up of water (and amine)
Take care interpreting the absolute value of the measured sizes due to dilution!
12
Challenge of the ELPI measurement = effect of dilution on measured size distribution:
Dilution necessary to avoid water condensation on the different ELPI+ stages electrical shortcutting! Dilution has effect (shrinking) on aerosol size distribution if aerosols contain a lot of water! Dilution no effect if aerosols are close to dry droplet diameter or PM that contain no water!
Brachert, L., J. Mertens, P. Khakharia, A. Huizinga, E. Goetheer and K. Schaber, 2013. The Challenge of Measuring Sulfuric Acid Aerosol number concentration and size distribution using a Condensational Particle Counter (CPC) and an Electrical Low Pressure Impactor (ELPI+). Journal of aerosol science, in review
13
Materials and methods used
On-line measurement of organics (MEA, aldehydes,…) and inorganics (NH3, CO2, H20, …) at ppm level FTIR
Off-line measurement of the gas phase: mostly used for NH3, MEA, aldehydes, nitrosamines Manual sampling
14
Challenges: Many components at different concentration levels (ppb – ppm)
Water saturated flue gases
Emissions possibly under aerosol form
No standardized methodology for manual sampling and consequent analysis of the gas phase in PCCC
SAM
PLIN
G
•Iso-kinetics
•Flow rate
•Set-up
•Ad-/Absorbent
•Sampling time SAM
PLE
STO
RAG
E
•Temperature
•Time
•Type of sampling container
ANAL
YSIS
•Method
•Limit of Detection
•Limit Of Quantification
•Sensitivity
•Accuracy
3 aspects to be considered for an accurate and precise measurement:
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Significant discrepancies observed at several sites between FTIR and manual measurements & amongst manual measurements
0
10
20
30
40
50
60
70
80
90
100
2:24:00 PM 7:12:00 PM 12:00:00 AM 4:48:00 AM 9:36:00 AM 2:24:00 PM 7:12:00 PM
Mon
eEth
anol
Amin
e (i
n %
of m
axim
um v
alue
)
MEA (FTIR)
MEA (lab 1)
MEA (lab 2, impinger)
MEA (lab 2, TD tube)
16
MEA analysis accuracy depends on the analytical method, the chemical concentration and matrix effect
Round Robin Test results for MEA (Care, only based on 1 RRT):
One laboratory gives unsatisfactory results As the matrix is getting more complex, higher deviations are
observed for all laboratories
-100%
-80%
-60%
-40%
-20%
0%
20%
40%
60%
A B C D
% o
f rea
ltive
err
or
MEA (100 ppm)
NH3 (10 ppm) + MEA (100 ppm) + volatile amines (10 ppm)
NH3 (100 ppm) + MEA (10 ppm) + volatile amines (1 ppm)
17
Effect of the sampling flow rate
Washing Section
LOW FLOW Absorbing solution
Oven
80 °C Small pump (3 l/min)
Ice Bath
Gas counter
Silica gel
Main gas flow
bubblers
180 °CFTIR
HIGH FLOW Absorbing solution
Oven
80 °C Pump (10 l/min)
Ice Bath
Gas counter
Silica gel
impingers
FID180 °C
bubbler
impinger
18
High Flow
Low Flow
Effect of sampling flow rate
FTIR
19
0
10
20
30
40
50
60
70
80
90
100
Test 2 -Low Flow
Test 3 -High Flow
FTIR
A
C
D
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Test 1 -Low Flow
MEA
em
issi
ons
(% m
axim
um v
alue
)
Effect of sampling on MEA emissions
Without MEA aerosols
With MEA aerosols
In absence of aerosols, MEA measured concentration are higher than compared to FTIR but same order of magnitude between laboratories
In presence of aerosols, MEA measured concentration are much lower than compared to FTIR but increases when increasing the sampling flow rate
Improved capture efficiency when using impingers instead of bubblers and the higher flow
Possible explanations:
⇒ In the manual sampling set-up, a part of the aerosols travels without being captured contrary to FTIR where all aerosols are evaporated at 180 C.
⇒ Overestimation by FTIR in the high MEA value range ? (only calibrated up to 55 mg.Nm-3)
20
Conclusions & future research
Amine aerosol formation is linked to the number of PM/aerosols entering the absorber Aerosols grow as they move through the absorber taking up water (and amine) Accuracy of MEA and NH3 measurements is function of the matrix
⇒ Cross-checking of laboratories measurement recommended ⇒ Spiked solution
In presence of aerosols, high discrepancy between FTIR and manual measurements are noticed
⇒ Aerosols potentially travel across the manual samplings set-up without being captured
21
Conclusions & future research
Characterize further the size and number of aerosols that enter and leave the absorber at different sites and their relation with MEA emissions The effect of the capture plant’s operational settings to minimise aerosol emissions Further evaluation of flue gas filters and their effectiveness in avoiding aerosol emissions Standardisation work is urgently needed for the emission monitoring in CCS
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