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Method for HCL Monitoring by FTIR Analysis

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Method used to monitor HCL using a FTIR instrument.

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Method for HCL Monitoring by FTIR Analysis

  1. 1. MKS Analytical Method for HCl by FTIR
  2. 2. FTIR Analysis MethodAnalytical Method– Classical Least Squares [CLS]– Predict chemical concentrations using spectroscopy (FTIR) and linear algebraCalibration Method– Requires certified gas or liquid standard – NIST Traceable– Collect signal/spectrum from FTIR– Combine and model using CLS– Analysis Region dependant upon component concentrationDetermining Sample Gas Concentration– Run sample gas through FTIR gas cell– Collect signal/spectrum from FTIR– Use calibration model to predict sample gas concentration 2
  3. 3. Calibration SummaryRegion Selection– Select ALL regions where compound is present in the spectrumAnalysis Band– Select the largest peak region– Modify Analysis Band Other compounds present in Sample Gas and interfere Bulk gas or another component fully overlaps any of the analysis region. 3
  4. 4. NO Calibration Regions 4
  5. 5. NO Calibration 5
  6. 6. Machine Independent Calibration 31 3 30 2.5% 4 29 5 2.0%28 6 1.5% Easily able to transfer calibrations from one 1.0% instrument to another 0.5% 0.0%22 12 Instrument to Instrument Variation Based on Ethylene Measurements 21 13 (years 2000 - 2002) 20 14 Demonstration of instrument to instrument variability 6 none of these instruments calibrated for Ethylene
  7. 7. Analytical Interference RemovalRegions Change with Concentration– Change Analysis RegionsHigher resolution allows analysis in the presence ofthe interference (usually H20)Spectral Interference Correction (H2O)– Mask Interferences (‘picket fencing’) 7
  8. 8. Different Regions for Different Concentrations 20% CO28% CO 100 ppm CO 8
  9. 9. Low Resolution (2.0 cm-1) Sample H2O NOExample of catalyst performance evaluationFigure used with permission from Johnson Matthey plc, Wayne, PA 9
  10. 10. High Resolution (0.5 cm-1) Sample H2O NOExample of catalyst performance evaluationFigure used with permission from Johnson Matthey plc, Wayne, PA 10
  11. 11. Removing H2O Interference 11
  12. 12. Removing H2O NO WaterSample 150ppm NO in 35% H2O (white) 35% H2O (red) Sample minus H2O (white) NO calibration (green) 12
  13. 13. No interference of water High sensitivityLow detection limits No artificial bias even in very high water (up to 40%) 13
  14. 14. Reduction of Sampling System InterferencesSample Line TemperatureSample PressureReactive ComponentsMaterial Selection 14
  15. 15. FT-IR Sampling SystemHeated Probe with filtering – Metal or Glass – <0.1 um recommended (must keep particulate low)Heated Sampling Line – MKS recommends SS not Teflon for most Apps – Minimum length as possible – Maintain Temp – 191 C normally – Maintain Pressure – 1.0 Atm (+/- 5% recommended)Sampling Pump – Before or After FT-IR Gas Analyzer Before be careful about contamination or sample loss After be careful not to let pressure go to low – Additional Filtering Possible if before 15
  16. 16. Field Deployable FTIR Heated Lines Sampling System Heated Probe Filter BoxStack On-Off Valve Rotometer FTIR Gas Analyzer Cylinder Spike Standard with SF6 Tracer Spike Recovery: cal gas 10% total flow Calibrated Gas Run: cal gas 7 lpm if pump pulls 5 lpm 16
  17. 17. Portland Cement Plants Continuous Emission MonitoringNational Emission Standards for Hazardous AirPollutants From the Portland Cement ManufacturingIndustry (40 CFR 63 SUBPART LLL)– Maximum Achievable Control Technology (MACT) Standards First EPA mandated National Limits to Reduce Mercury and Other Toxic Emissions from Cement Plants EPA issued final Portland Cement MACT in September 2010Components required– NOx, SO2, HCl, CO, CO2, PM, THC, mercury 17
  18. 18. HCl Measurements with FTIREPA Method 321– “Measurement of Gaseous Hydrogen Chloride Emissions At Portland Cement Kilns by Fourier Transform Infrared (FTIR) Spectroscopy”– Isolated sample analysisEPA Method 7E– “Determination of Nitrogen Oxides Emissions From Stationary Sources (Instrumental Analyzer Procedure)”– Describes general measurements requirements for all gases when using a continuous instrumental analyzer 18
  19. 19. HCl Measurements with FTIRSample (white)with 5 ppm HCland 12% water(red) H2O subtraction HCl peaks clearly visible after H2O subtraction 19
  20. 20. HCl Measurements with FTIR (2) HCl calibration peaks (red and green) HCl subtractionAfter HClsubtraction,only noise left 20
  21. 21. No Interference of Water High SensitivityH2O stepsup to 40% Lowdetection limits No artificial bias even in very high water (up to 40%) 21
  22. 22. MG2030 CEM Ranges and Detection Limits Component ppm mg/m3CH4 0 - 21 0 - 15CH4 0 - 70 0 - 50CO 0 - 60 0 - 75CO 0 - 120 0 - 150 Component Detection limitCO 0 - 1200 0 - 1500 CH4 0.3 ppmCO2 25% 25% CO 0.5 ppmH2O 40% 40% CO2 0.025%HCl 0-9 0 - 15HCl 0 - 55 0 - 90 H2O 0.25%HCl 0 - 123 0 - 200 HCl 0.20 ppmHF 0 - 11 0 - 10 HF 0.25 ppmN2O 0 - 26 0 - 50 N2O 0.1 ppmN2O 0 - 51 0 - 100N2O 0 - 255 0 - 500 NH3 0.35 ppmNH3 0 - 13 0 - 10 NO 0.5 ppmNH3 0 - 99 0 - 75 NO2 0.4 ppmNO 0 - 149 0 - 200 SO2 0.6 ppmNO 0 - 299 0 - 400NO 0 - 1119 0 - 1500NO2 0 - 24 0 - 50NO2 0 - 49 0 - 100NO2 0 - 488 0 - 1000SO2 0 - 26 0 - 75SO2 0 - 105 0 - 300SO2 0 - 699 0 - 2000 22
  23. 23. Solution for Compliance of Portland Cement PlantsFTIR designed for Continuous Emission Monitoring– Thermoelectric detector, no need of liquid N2HCl detection limit of 0.2 ppm– Calculated as 3-sigma in 25% H2OTypical Gases and Ranges– CH4 0-21 ppm 0-70 ppm– CO 0-60 ppm 0-1200 ppm– CO2 0-25% (soon to 40%)– NOx 0-149 ppm 0-300 ppm– SO2 0-26 ppm 0-699 ppm– H2O 0-40%– HCl 0-9 ppm 0-55 ppmFTIR associated with FID (THC), PM and mercurysensors for complete solution 23
  24. 24. Why MKS Over Competitors
  25. 25. CEM FTIRAdvantages– Multiple species – one instrument SO2, NH3, NO, HCl, HF, CO, CO2, H2O, and VOCs– Analyze components in high CO2 and H2O– Direct analysis – no chemical conversion or “fudge factors”– Analysis method minimizes interferents– Flexibility in Changing in Method Customer can easily modify 25
  26. 26. WHY MKS?Fastest Acquisition with High Resolution (0.5cm-1)Smallest gas cell volume with long pathlength– 200 mL for 5.11m PathProcess Instrument– Not a Lab system converted to Process– Engineered for Process Environment– Gas Cell integrated heaters and pressure controllerProvide Method Development as well as CustomerSupport 26

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