september 13-14, 2012 | santa ana, california · september 13-14, 2012 | santa ana, california ftir...
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CEMTEK ENVIRONMENTAL’S CEMTEK ENVIRONMENTAL’S
2012 EMISSIONS MONITORING SEMINAR & TRAINING SESSION2012 EMISSIONS MONITORING SEMINAR & TRAINING SESSIONSeptember 13-14, 2012 | Santa Ana, Californiap |
FTIR Systems & OperationFTIR Systems & Operation
INDUSTRIAL MONITOR AND CONTROL CORP.
CEMTEK ENVIRONMENTAL’S 2012 EMISSIONS MONITORING SEMINAR & TRAINING SESSION
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Basic Concepts of Basic Concepts of Optical Optical DetectionDetection
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Active & Passive Open Path FTIRActive & Passive Open Path FTIRActive & Passive Open Path FTIRActive & Passive Open Path FTIR
• Active transmission mode uses a light source in the• Active transmission mode uses a light source in the FTIR which is modulated by the instrument and is then transmitted through the gas to be monitored.
• The transmitted beam is captured and analyzed to determine the compounds present and their
t ticoncentrations.
• Analysis is done using reference standards for each compound collected under controlled conditions of:compound collected under controlled conditions of: concentration, temperature, pressure, and path length
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Typical Extractive FTIR SystemTypical Extractive FTIR System
DetectorControl and
Reduction
FTIRComputer
Input from stack or ambient air
Multi‐passWhite Cell60 20060cm‐200mpath
ExhaustHeated or ambientextraction line
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Pump
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Basic ConceptsBasic Conceptspp
Most molecules absorb infrared (IR) lightMost molecules absorb infrared (IR) light- The patterns of IR wavelengths (colors) they absorb are
unique to each molecule- The amount of light they absorb is proportional to
their concentration
As a Result:
- The presence of specific compounds can be unequivocallydetermined by the absorption patterns
As a Result:
- The concentration of the compounds can be measured by thestrength of the absorption patterns
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Infrared Absorbance Spectra of Select CompoundsInfrared Absorbance Spectra of Select Compounds
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What About OverlappingWhat About OverlappingFeatures?Features?Features?Features?
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Infrared Absorbance Spectra of Select CompoundsInfrared Absorbance Spectra of Select Compounds
Overlapped Spectra
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Overlapped Spectra of NOOverlapped Spectra of NO22 and NHand NH33
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Wh t C AWh t C AWhat Can An What Can An FTIR MonitorFTIR Monitor
Measure ?Measure ?
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Compounds CoveredCompounds Coveredpp
• The FTIR can monitor most molecular species• The FTIR can monitor most molecular species except for homonuclear diatomics (Cl2, H2, O2, N2, etc.) 2, )
• The detection limit varies by compound but allThe detection limit varies by compound but all can be detected to sub ppm-levels with small systems and to the low ppb-level with larger systems
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Detection Limits Detection Limits
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Detection Limits Detection Limits
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Basic EquationsBasic EquationsT i i M dT i i M dTransmission ModeTransmission Mode
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Transmittance of an Absorption CellTransmittance of an Absorption Cell
Absorption CellIo ( ) I( )
Absorption Cell
0%= {I
=( )( )
100%= {Io=( )
( )
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Transmittance for MoleculesTransmittance for Molecules
) I( )/I ( )) = I()/Io() C L= e ‐ C L
Where:
k(n) = the gas absorption coefficient
C th t tiC = the gas concentration
L = The optical path length
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Transmittance for Molecules (cont.)Transmittance for Molecules (cont.)
{ t ( ) }Absorbance = - log10 { t (n) }
= ‐ log10 {e ‐ C L}
= (0.434) C L
Scales as concentration times path length
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Scales as concentration times path length
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Transmittance Spectrum of HCNTransmittance Spectrum of HCN
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Absorbance Spectrum of HCNAbsorbance Spectrum of HCN
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Measured Spectra of Phenol at Various ConcentrationsMeasured Spectra of Phenol at Various Concentrations
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The The Fourier Fourier Transform Transform Infrared SystemInfrared System
(FTIR)(FTIR)(FTIR) (FTIR)
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Schematic of FTIR ModulatorSchematic of FTIR Modulator
Fi d Mi
Moving Mirror
Fixed Mirror
CollimatingMirror
BeamBeamsplitter
Waveform Addition
Aperture
Focusing
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FocusingMirror IR
Source
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Typical FTIR Typical FTIR InterferogramInterferogram Near Center BurstNear Center Burst
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InterferogramInterferogram & Absorbance Spectrum From FTIR& Absorbance Spectrum From FTIR
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The FTIR ProcessingThe FTIR ProcessingSequenceSequence
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FTIR Processing Sequence FTIR Processing Sequence
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B i C t fB i C t fBasic Concepts of Basic Concepts of FTIRFTIR AnalysisAnalysisFTIR FTIR AnalysisAnalysis
------Cl i l L t SCl i l L t SClassical Least SquaresClassical Least Squares
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Linear Least Linear Least SquaresSquares Regions and Regions and ComponentsComponents
Region
743 50 I S I743.50 I ‐ S ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ I ‐ ‐ ‐
766.25 I ‐ I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S ‐ ‐ ‐ ‐ ‐ ‐
889.50 I ‐ ‐ I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S ‐ ‐ ‐ ‐ ‐ ‐ ‐
937 50 S I S S S S937.50 S ‐ I S ‐ S S ‐ ‐ ‐ ‐ S ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐
1009.00 I ‐ ‐ I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S ‐ ‐ ‐
1035.50 I ‐ I I ‐ ‐ ‐ ‐ S S S ‐ ‐ ‐ ‐ ‐ I ‐ ‐ ‐
1095.00 I ‐ ‐ I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S ‐ ‐ ‐ ‐ ‐1095.00 I I S
1148.00 I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S
1900.00 I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S ‐
2138.50 I S I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐
2207.50 I I I ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ S ‐ ‐
2787.00 I ‐ ‐ ‐ I ‐ ‐ S I ‐ ‐ ‐ ‐ ‐ ‐ S ‐ ‐ ‐ ‐
2932.50 I ‐ ‐ ‐ S ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐
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Observed SpectrumObserved SpectrumHouston, Texas 15 April 1991Houston, Texas 15 April 1991
Sample Clean Air
0.3
0.35
0.25
0.3
0.2
0.25
0.15
0.2
0.25
rban
ce
0 05
0.1
0.15
0.05
0.1
Abs
o
l
0
0.05
860 872 884 896 908 920 932 944 957 969 981 993-0.05
0
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0.5 cm‐1 resolution Wavenumber (cm-1)
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Observed SpectrumObserved SpectrumHouston, Texas 15 April 1991Houston, Texas 15 April 1991, p, p
0.35
Sample Clean Air
0.25
0.3
0 2
0.25
0.3
e
0.15
0.2
0.1
0.15
0.2
Abs
orba
nce
0.05
0.1
0
0.05
A
0 5 cm‐1 resolution
0860 872 884 896 908 920 932 944 957 969 981 993
-0.05
Wavenumber (cm-1)
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0.5 cm 1 resolution
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Difference SpectrumDifference SpectrumReference File OverlaysReference File Overlays
Data C3H6 Isobut CO2
Reference File OverlaysReference File Overlays
0.1
0.12
0.1
0.12
0.06
0.08
orba
nce
0.06
0.08
0.02
0.04Abs
o
0
0.02
0.04
l
0860.37 884.47 908.57 932.67 956.77 980.87
Wavenumber (cm 1)
-0.02
0
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0.5 cm‐1 resolution Wavenumber (cm-1)
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Difference SpectrumDifference SpectrumReference File OverlaysReference File Overlays
Data C3H6 Isobut CO2
Reference File OverlaysReference File Overlays
0.1
0.12
0.1
0.12
0.06
0.08
orba
nce
0.06
0.08
0.02
0.04Abs
o
0
0.02
0.04
0860.37 884.47 908.57 932.67 956.77 980.87
Wavenumber (cm 1)
-0.02
0
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0.5 cm‐1 resolution Wavenumber (cm-1)
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Difference SpectrumDifference SpectrumReference File OverlaysReference File Overlays
Data C3H6 Isobut CO2
Reference File OverlaysReference File Overlays
0.1
0.12
0.1
0.12
0.06
0.08
orba
nce
0 04
0.06
0.08
0.02
0.04Abs
o
0
0.02
0.04
0 5 cm‐1 resolution
0860.37 884.47 908.57 932.67 956.77 980.87
Wavenumber (cm-1)
-0.02
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0.5 cm 1 resolution Wavenumber (cm-1)
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Difference SpectrumDifference SpectrumReference File OverlaysReference File Overlays
Data C3H6 Isobut CO2
Reference File OverlaysReference File Overlays
0.1
0.12
0.1
0.12
0.06
0.08
orba
nce
0 04
0.06
0.08
0.02
0.04Abs
o
0
0.02
0.04
0860.37 884.47 908.57 932.67 956.77 980.87
Wavenumber (cm-1)
-0.02
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0.5 cm‐1 resolutionWavenumber (cm 1)
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The The ImaccImacc FTIR FTIR MonitorsMonitors
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The Base UnitThe Base Unit
The unit utilizes a 0.125 cm-1 “dash-pot” interferometer with “dynamic alignment” both of which provide stabilitywith “dynamic alignment” both of which provide stability critical for field work
– The “dash pot” consists of a graphite piston running in a precision glass tube, it has only one degree of freedom and as a result is very stable and immune to vibration
– The “dynamic alignment” is laser controlled and actively aligns the FTIR thousands of times per second providing additionaltimes per second providing additional immunity to vibration and temperature variations
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Base Unit AccessoriesBase Unit Accessories
• The modular arrangement allows use of both cell• The modular arrangement allows use of both cell-based and open-path accessories with one base unit
• The cell-based accessories are used for extractiveThe cell based accessories are used for extractivemonitoring in: ambient air, industrial process streams, stacks, or abatement systems
• The telescope-based accessories are used for open-path monitoring in: the ambient air, at the fence-line, or around process areasor around process areas
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Cell Based AccessoriesCell Based Accessories
The cell-based accessories use heated cells and extraction lines at temperatures up to 200°C, allowing for monitoring of saturated process streams (hot/wet).
Typical cell accessories include: Typical cell accessories include:– Fixed path cells: 5 cm and 10 cm (% concentrations)– Variable path cellsVariable path cells
1 m to 10 m cell (0.1 ppm)4 m to 32 m cell (20 to 50 ppb)12 m to 80 m cell (3 to 10 ppb)24 m to 150 m cell (1-5 ppb)
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Shell CellShell Cell--Based MonitorBased Monitor
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InteriorInterior of Shell System
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LowerLower--LevelLevel FTIR ModulatorFTIR Modulator
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UpperUpper--Level Cell and DetectorLevel Cell and Detector
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Passive FTIR OperationPassive FTIR Operation
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Passive FTIR RadiometerPassive FTIR Radiometer
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Passive OpenPassive Open--Path SignaturesPath Signatures
• Any hot gas emits infrared with exactly the same y g ypattern that it has in absorption
Th f i i i i t b• Therefore species in emission spectra can be identified and quantitated in the same manner as they are in absorption spectroscopy
• However
• The strength of emission is proportional to concentration as it is in absorption spectra but also to the temperature of the gas
CEMTEK ENVIRONMENTAL’S 2012 EMISSIONS MONITORING SEMINAR & TRAINING SESSION
to the temperature of the gas.
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Hardware - Passive FTIR At Flare Test
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The Signal Observedg
BackgroundRadiance
FlareRadiance The FTIR Signal arises from Four elements:
•The Total FTIR Signal M is then:
AtmosphericTransmission& Radiance
•Background radiance•Flare radiance•Atmospheric Transmission and Radiance
The Total FTIR Signal Mp is then:Rb * plume atm + Rp * atm + Ratm + Rftir
The FTIR signal can be reduced to:( ) C lM M( )
)(p b
pnb
pairbb
Cal
CalM MR M M
L
Mp = The measured plume radianceMb = The measured background radianceMn = The measured cold source backgroundLpbb = The Planck function at temperature of plumeCal = The system calibration function
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Cal = The system calibration functionair = Air Transmission
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Flare Efficiency
1
y
0.995
%)
Moderate Over
0.985
0.99
ffici
ency
(%
Heavier OverSteaming
Moderate Over Steaming
0 975
0.98
Ef Steaming
0.97
0.975
8:00 9:00 10:00 11:00 12:00 13:00
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8:00 9:00 10:00 11:00 12:00 13:00Time
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Extractive Probe Used in TCEQ Flare Validation Test
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CE vs. CZG NHV - All TCEQ Steam
100%
70%
80%
90%
y (%
)
50%
60%
ion Efficiency
TCEQ 20:80 TNG to Propylene (S3 S4 S5 S6)
20%
30%
40%
Combu
sti TCEQ 20:80 TNG to Propylene (S3,S4,S5,S6)
TCEQ 20:80 TNG to Propylene (S7,S8,S9,S10,S11)
TCEQ 100% Propane (S12,S13,S14)
0%
10%
0 50 100 150 200 250 300 350 400 450 500C b ti Z G N t H ti V l (H 1212 BTU/ f) (BTU/ f)
CEMTEK ENVIRONMENTAL’S 2012 EMISSIONS MONITORING SEMINAR & TRAINING SESSION
Combustion Zone Gas Net Heating Value (H2=1212 BTU/scf) (BTU/scf)
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CE vs. CZG NHV - All TCEQ Steam
100%
70%
80%
90%
100%
y (%
)
40%
50%
60%
70%
ion Efficiency
TCEQ 20:80 TNG to Propylene (S3,S4,S5,S6)
TCEQ 20:80 TNG to Propylene (S7,S8,S9,S10,S11)
20%
30%
40%
Combu
sti
TCEQ 100% Propane (S12,S13,S14)
TCEQ Extractive
0%
10%
0 50 100 150 200 250 300 350 400 450 500Combustion Zone Gas Net Heating Value (H2=1212 BTU/scf) (BTU/scf)
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