Monitoring and impacting gaseous emissions in post combustion carbon capture Jan Mertens a *, Marie-Laure Thielens a, Jacob Knudsen b and Jimmy Andersen b a Laborelec, Rodestraat 125, 1630 Linkebeek, Belgium b DONG Energy, Amerikavej 7, DK-6700 Esbjerg, Denmark Presentation at the IEAGHG 1st Post Combustion Capture Conference, Abu Dhabi, 18 May 2011 * Jan.Mertens@laborelec.com
Objective & Outline Objective: Present an on-line monitoring technique (FTIR) and its utility in understanding emissions and their relation to plant operational settings Outline: Challenges in emission monitoring in PCCC Fourier Transform Infra Red (FTIR) spectroscopy Sampling set-up Comparison to Flame Ionisation Detector (FID) and manual meas. Linking emissions to CC pilot plant s operational settings Conclusions & Future research 2
Challenges in emission monitoring in PCCC Top of absorber: * high humidity (water saturated at around 50 C) * low temperatures Risk of loosing water soluble components Water = interferent in many measurement techniques 3
Challenges in emission monitoring in PCCC Focus of this presentation Top of absorber: * high humidity (water saturated at around 50 C) * low temperatures Risk of loosing water soluble components Water = interferent in many measurement techniques Top of stripper: * high CO 2 (> 99 vol%) CO 2 = interferent in many measurement techniques 4
Fourier Transform Infra Red (FTIR) spectroscopy Traditional IR (GFC) Measures only separate wavelength bands with gas-filled filters Multiple gases can be measured with additional filters (typically maximum 6 gases) Broad band light source Optical filters Sample cell B Fourier Transform Infrared (FTIR) Spectrometer measures all the IR wavelengths simultaneously A B C Any number of components (up to 50) can be analysed from single measurement Interferometer 5
Sampling set-up HOT (80-180 C ) AND WET sampling system: sampling probe, line, pump, filter and FTIR analyser itself (at 180 C) no drying/dilution Temperature = f(heated sampling line length) compromise between possible amine degradation and avoid droplets (aerosols) reaching the analyser 6
Sampling set-up Simultaneous organic and inorganic substances at ppm level! Current database includes: CO CO 2 HCl HF H 2 O NO NO 2 N 2 O NH 3 SO 2 acetaldehyde aceton Formaldehyde AMP (2-amino-2-methylpropanol) DEA (diethanolamine) DGA (diglycolamine) DMEA (dimethylethanolamine) MDEA (n-methyldiethanolamine) MEA (monoethanolamine) PZ (piperazine) Detection limit is f(component, matrix) and typically ranges between 0.2 and 2 mg m -3 7
Comparison to Flame Ionisation Detector (FID) meas. Since the on-site application of FTIR in this area is challenging (high humidity, low temperature), validation is necessary! COMPARISON between FTIR & FID (= Standard equipment for measuring Total Organic Carbon (TOC) in flue gas) COMPARISON between FTIR & manual measurements 8
Comparison to Flame Ionisation Detector (FID) meas. FID = measure for Total Organic Carbon (TOC) 80 Total Organic Carbon expressed as mg C Nm -3 (%) 60 40 20 Y = 0.80 X + 0.82 R2 = 0.92 FID response factor (RF) of 0.8 agrees with literature values for many amines 0 0 20 40 60 80 100 AMP + PZ expressed as mg C Nm -3 (%) 9
Comparison to manual measurements Typical set-up: Pump for isokineticisme 80 C 80 C Oven containing filter 60 C Oven containing sorbent tubes Sorbent tubes Water trap Water trap Water trap Small pump (1.5 l/min) Small pump (1.5 l/min) Small pump (1.5 l/min) 10 Ice Bath Chemical filled
Comparison to manual measurements Good agreement for NH 3 and some of the amines Discrepancies amongst manual measurements using different sampling techniques (eg. presence of filters, sorbents, presence of water traps, ) have been noticed Experience learns that SAMPLING and consequent sample handling and storage = CRUCIAL for a good measurement! There is a clear need for more research and standardisation work to be done on this topic! 11
Linking emissions to CC pilot plant s operational settings Decreasing absorber outlet temperature (AMP): 100 temp out of washing section AMP 56 AMP concentration (%) 80 60 40 20 52 48 44 40 36 Tempeture out of washing section ( C) No longer closed water balance (T out < T in ) 0 32 8:18 11:38 14:57 18:17 21:38 Time 12
Linking emissions to CC pilot plant s operational settings Decreasing absorber outlet temperature (MEA & NH 3 ): 100 80 NH3 MEA T out 55 50 Effect on NH 3, only temporary Effect on MEA less obvious NH 3 and MEA (%) 60 40 20 45 40 35 T ( C) in emission behaviour and reaction to operational settings amongst different amines = f(areosols)?? 0 30 8:00 9:30 11:00 12:30 14:00 Time 13
Linking emissions to CC pilot plant s operational settings Decreasing solvent inlet temperature: 60 100 Temperature ( O C) 50 40 80 60 AMP concentration (%) Large T difference between in and out of washing section essential for a good washing! 30 20 Temp. into washing section temp. out of washing section Inlet solvent temperature AMP 40 20 10:58 12:39 14:19 14 15:58 Time
Linking emissions to CC pilot plant s operational settings CO 2, in T diff. over wash section (exotherm) AMP : Temperature difference over washing section influences the emissions! Possibly additional effect of less free amine when high [CO 15 2 ] and thus reduction in volatility!
Linking emissions to CC pilot plant s operational settings Positive correlation tendency between oxygen and ammonia (MEA campaign): 100 80 NH 3 concentration (%) 60 40 Correlation coefficient of only 0.49 20 0 4 6 8 10 12 O 2 content (vol%) 16
Conclusions FTIR suitable for monitoring organic and inorganic emissions from PCCC at ppm level On-line monitoring allows(as compared to off-line): * Relating the emissions to PCCC operational plant settings and thus controlling the emissions * Identifying different emission behaviour between different components 17
Future research There is a clear need for more research and standardisation work with respect to manual emission measurements from PCCC Research the different emission behaviour between different amines and its relation to aerosol formation. Need for iso-kinetic on-line monitoring? Research with respect to suitability of on-line techniques for monitoring organics at ppb or ppt level is needed 18
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