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Ultra Low Level HCl CEMs for Coal Combustion Facilities Using FTIR and Associated Performance Specifications MKS Instruments On-Line Product Group 2 Tech.

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Presentation on theme: "Ultra Low Level HCl CEMs for Coal Combustion Facilities Using FTIR and Associated Performance Specifications MKS Instruments On-Line Product Group 2 Tech."— Presentation transcript:

1 Ultra Low Level HCl CEMs for Coal Combustion Facilities Using FTIR and Associated Performance Specifications MKS Instruments On-Line Product Group 2 Tech Drive, Suite 201 Andover, MA 01810 Tel: 978-482-5364 MultiGas™ FT-IR Automated HCl CEM Systems California Desert Air Working Group November 13-14, 2013 Las Vegas, NV Peter G. Zemek, Ph.D.

2 Discussion 40 CFR Parts 60 and 63 - (NESHAP) for the Portland Cement Manufacturing Industry and Standards of Performance for Portland Cement Plants - Meet Standard by 2015 EPA Utility MACT (40 CFR Part60, Subpart UUUUU, EPA – 1,350 Units Affected Continuous Monitoring (HCl) from new and existing coal and oil- fired (HF) emissions Cement - 3 ppmv HCl, (3.8 mg/M 3 @ 7% O2), EGU – 1 ppmv HCl –Instrument HCl Quantification - Rule of Thumb 20% below Emissions Regulation, So need 0.2 ppm Current MKS FTIR is 50 ppb Use Performance Specification 15, App B and Procedure 1 of Appendix F until new PS (20 yrs. old) New PS-18 in development specific to HCl (Spring 2014) –Initial Instrument Qualification –On-going QC promulgated separately MKS Instruments 2

3 Performance Specifications for FTIR CEMS PS-15 For Extractive FTIR CEM Systems in Stationary Sources Reference Method RATA Run Comparisons – Follow PS 2 Specifications and Test Procedures for SO2 and NOX CEM in Stationary Sources – WILL BE CHANGED (M320/ASTM D6348-12) Draft PS-18 and Test Procedures for HCl CEMS in Stationary Sources - Spring 2014 Tests on-going at EPA RTP-NC NIST traceable standards now available 1-20 ppmv Bal N2. EPA has a 1 ppm NIST traceable standard. We match against HITRAN - High Resolution Transmission -Air Force Research Laboratories (1960s) Harvard-Smithsonian Center for Astrophysics, Cambridge MA, USA. Worldwide standard of atmospheric molecular transmission and region of the EM spectrum

4 FTIR Reference Methods for CEMS Validation and RATA Reference Methods: Method 301—Field Validation of Pollutant Measurement Methods From Various Waste Media Method 320* - Measurement of Vapor Phase Organic and Inorganic Emissions by Extractive (FTIR) (Includes FTIR Protocol) Method 321** - Measurement of Gaseous HCl Emissions at Portland Cement Kilns by FTIR Spectroscopy ASTM D6348-12 Standard Test Method for Determination of Gaseous Compounds by Extractive Direct Interface Fourier Transform Infrared (FTIR) Spectroscopy *1 of 2 RM for EGU **Only acceptable RM for Portland Cement MACT

5 Validation and On-Going HCl CEM PS-18 1. Before Installation, instrument manufacturer must perform: a.Linearity b.Detection Limit c.Cross Sensitivity 2. After Installation to Validate must perform: a.RATA Test on Other than HCl compounds b.Reference Method Test HCl - EPA-M321 RATA a. Includes Dynamic Spike c.7 day drift test 3. Daily and On-Going (all automated) a.Zero b.Dynamic Spike or Dry Cal Span (Wet or Dry) c.Periodic RATA d.Provide 30 day rolling avg HCl MKS Instruments 5

6 Advantages of FTIR Measurements done Hot-Wet –Required for polar components HCl, HF –Works with High CO 2 and H 2 O –No Chemical Conversions Multiple components Simultaneously –THCs, HCl, HF, VOCs, NOx, SO 2, etc. –Additional components: No hardware change Can be added in the field Simple Operation –No daily maintenance –No Daily Calibration –High sensitivity gas cell small volume (200mL) long path length (5.11m) No training needed –Software alerts to any malfunction –Only laser replace and cell cleaning Fast (1 Hz or 5 Hz)

7 7

8 MKS Confidential 8 What is FTIR? Fourier Transform Infrared Spectroscopy (Spectrometry) –Fourier Transform: mathematical conversion from the time domain to the frequency domain –Infrared: Low energy wavelengths longer than visible light (heat) –Spectroscopy: study of the electromagnetic spectrums electrical and magnetic fields FTIR uses an “Interferometer” -- a device which splits focused light, optically retards it and recombines it to produce an optical interference pattern resulting in an Interferogram. A computer converts the Interferogram to an Absorbance spectrum which is Linear

9 MKS Confidential 9 MKS IR Spectroscopy Hardware Source: Blackbody (Hot Silicon Carbide ~ 1300 K) Modulator: Interferometer Sample: Vapor (Gas Cell, 10, 5.11m, 35cm, or 2cm path lengths) Detector: Mercury Cadmium Telluride (MCT) Quantum Detector cooled by Thermoelectrically (TE) Peltier

10 MKS Confidential 10 IR Source To Gas Cell & Detector Beamsplitter Moving Mirror Fixed Mirror HeNe Laser monochromatic light Creating the Interferogram The FT-IR Light Modulator

11 MKS Confidential 11 FTIR From Igram to Spectrum 1. Create Interferogram then send to detector (Modulator) 2. Amplify Interferogram (preamp) then digitize it (A/D converter) 3. Send digital signal to computer (PC) 4. Apply Fourier Transform math to Interferogram, result is Spectrum ( I ) 5. Remove background noise signals ( Io ) from Sample ( I ) 6. Result is Absorbance gas spectrum ( A ) used to identify the different species

12 MKS Confidential 12 Background and Sample BACKGROUND (Io) N 2 Purge SAMPLE (I) 1000 ppm NH 3 Absorbance = - Log (I/Io)

13 MKS Confidential 13 Absorbance is Proportional to Concentration FFT of Sample 1000 ppm NH 3 Absorbance = - Log (I/Io) Absorbance =  C path

14 MKS Confidential 14 FTIR Analysis Method Analytical Method –Classical Least Squares (CLS) then Beers Law, Abs = a b c  measured spectrum aabsorptivity coefficient or ε  from calibration bpath length  fixed (5.11 meter) c sample concentration (calculated)  what we want –Canned Method - No user input necessary –Hot and Wet, No sample change – No ionization –No pressure drop across sample cell –1 scan/second - 1 data point every 30 seconds –40 sample cell turnovers per minute –Self -validating sample method –Cement – Only acceptable reference method EPA M321

15 MKS Confidential 15 Classical Least Squares  Based on Beer’s Law  Relatively fast computationally  More complex mixtures  Wavelengths used need to be greater than #components  Noise reduced as # s increase 1 2 a b a+b WAVELENGTH ABSORBANCE CLS Spectral Analysis  Finds factors for all reference spectra in method/recipe to recreate the sample spectrum

16 Powerful Technique - CLS for HCl Measurements with FTIR Sample (white) with 5 ppm HCl and 12% water (red) HCl peaks clearly visible after H 2 O subtraction H2O subtraction 16

17 Powerful Technique - CLS for HCl Measurements with FTIR HCl calibration peaks (red and green) After HCl subtraction, only noise left HCl subtraction 17

18 Examples of Pre-Abatement Coal Fired (Cement Plant) Gas Concentrations Measured by FTIR Plant 1Plant 2Plant 3Plant 4Plant 5Plant 6 HCl5-3000-50-4<1 2-4 SO 2 0-600-2000-2400*300-400<1 NOx250-450*300-600100-400100-300~ 150~ 800 CH 2 O5-250-33-92-3~ 20~ 3 *NH 3 0-1500-400-800-50~300-15 CO200-400*100-600*100-200*100-600*~ 300300-700 CH 4 ~ 2 ~ 5 18 * Also includes periodic high concentration spikes All values in ppmv (or ppm) Includes data from non-US plants Concentration ranges e.g. min reading. Note: max reading, not rolling averages Data spanning few minutes to few days H 2 O and CO 2 also measured with targets (cost effective) * - Not measured with high sensitivity instrument (but can do high levels)

19 19 Time HCl Concentration (ppm) Examples of HCl Concentration Profiles at Cement Plants – RM On/Off Raw Mill OFF Raw Mill ON

20 TÜV ranges & uncertainties MKS 2030D TE9 CEM FTIR Gas comp. Cert. rangeSupp. range 1 Supp. range 2 ELVU/CU/C req. NH 3 0-10 mg/m 3 0-75 mg/m 3 -10 mg/m 3 6.2%30.0% CO 0-75 mg/m 3 0-300 mg/m 3 0-1500 mg/m 3 50 mg/m 3 6.2%7.5% SO 2 0-75 mg/m 3 0-300 mg/m 3 0-2000 mg/m 3 50 mg/m 3 7.0%15.0% NO 0-200 mg/m 3 0-400 mg/m 3 0-1500 mg/m 3 130 mg/m 3 6.8%15.0% NO 2 0-50 mg/m 3 0-100 mg/m 3 0-1000 mg/m 3 50 mg/m 3 4.1%15.0% HCl 0-15 mg/m 3 0-10 ppmv 0-90 mg/m 3 0-200 mg/m 3 10 mg/m 3 8.1%30.0% HF 0-3 mg/m 3 0-10 mg/m 3 -1 mg/m 3 19.3%30.0% CH 4 0-15 mg/m 3 0-50 mg/m 3 -10 mg/m 3 7.0%22.5% CO 2 0-25%-- 3.3%7.5% H2OH2O 0-40%-- 3.4%7.5% N2ON2O 0-50 mg/m 3 0-100 mg/m 3 0-500 mg/m 3 50 mg/m 3 4.5%15.0% 1 ppm HCl = 1.49 mg/m 3

21 FTIR Suppliers - TÜV Ranges & Uncertainties SO 2 Cert. rangeSupp. range 1Supp. range 2Rel. U/C MKS 0-75 mg/m 3 0-300 mg/m 3 0-2000 mg/m 3 7.0% of 50 mg/m 3 Comp 1 0-75 mg/m 3 0-300 mg/m 3 0-1500 mg/m 3 9.4% of 50 mg/m 3 Comp 2 0-75 mg/m 3 0-300 mg/m 3 0-1500 mg/m 3 10.5% of 50 mg/m 3 Comp 3 0-75 mg/m 3 0-300 mg/m 3 -9.4% of 50 mg/m 3 Comp 4 0-75 mg/m 3 0-300 mg/m 3 -11.5% of 50 mg/m 3 HCl Cert. rangeSupp. range 1Supp. range 2Rel. U/C MKS 0-15 mg/m 3 0-90 mg/m 3 0-200 mg/m 3 8.1% of 10 mg/m 3 Comp 1 0-15 mg/m 3 0-90 mg/m 3 -12.0% of 10 mg/m 3 Comp 2 0-15 mg/m 3 0-90 mg/m 3 0-150 mg/m 3 12.2% of 10 mg/m 3 Comp 3 0-15 mg/m 3 --12.8% of 10 mg/m 3 Comp 4 0-15 mg/m 3 0-90 mg/m 3 -11.4% of 10 mg/m 3

22 EPA Test Facility – PS18 RTP, NC MKS Reference Method -Anchor ORD’s Multi-Pollutant Combustion Research Facility –4M Btu/h down-fired combustor firing coal and/or NG –Multiple pollution control configurations possible SCR, ESP, FF, Wet Scrubber –Duct injection of gases to control emission profiles and combinations HCl, SO 2, NO x, CH 4, CO, NH 3, H 2 O, CH 2 O –All CEMS and RM measurements from same basic location 22

23 EPA REFERENCE METHODS – MKS FTIRs - Anchors for Testing (EPA and Industry) Looking at 3 different high resolution FTIR analyzers Focus on DLs, measurement quality and RM performance at very low HCl levels LN2, TE9, HS Point of reference for HCl Gas Standards 23

24 NEW: High-Sensitivity FTIR HCl Analyzer for CEM HCl detection limit 0.03 ppm (30 ppbv) plus bias Hot and Wet – 200mL Sample Volume No liquid nitrogen (LN2) needed No N 2 Background → easier integration than standard FTIR – turn on and go No Calibration Needed– “Canned” Method Can measure HCl, CH 2 O, HF, H 2 O, N 2 O, CH 4 with similar high sensitivity – or ELIMINATE Spectral Regions of no concern –hardware based 24

25 MKS Instruments 25 Installations - Two CEM systems two Cement Plants –Passed PS18 RATA 1 is almost 1 year old and 2 other HCl CEM going in -Two in Hildago, Mex. CEM PS-15 Cal Data 2 years Running

26 Transferrable Hardware & Software MKS Instruments 26

27 Detector/Hardware Influences High Sensitivity System HCl, HF, CH 4, H 2 O, N 2 O, CH 2 O MKS Instruments 27 TE9u CEM LN2-16u MCT (77K) TE-HS CEM Sensitivity (signal) S/N IR Band-pass Filters spectral region

28 MKS Instruments 28 EXAMPLE of No Cross Sensitivity No change in HCl concentration Spike @ 900 ppm CH 4 and 6% H 2 O

29 Staged Blowback Filtration 80 psig MKS Instruments 29

30 RM and PS18 require a Dynamic Spike Replace 10% CEM flow with spike material Spike10 x 50% of what’s found (3 ppm native, 15 ppm spike) Result Theoretical ~3+1.5 = 4.5 ppm HCl CEM Recovery +-20%, RM is 30% MKS FTIR CEM Data 15 Days

31 H 2 O vs. HCl in CEM Cement Extractive System No Filter Change or Blowback – 4 months CEM passes PS-15/Draft 18 with Sig Filter Cake, until Dry Gas is introduced Dropping H 2 O to < 0.5%, Filter cake sublimes to HCl gas, Conc. Inc. rapidly Then, comes back to Steady-State when H 2 O > 0.5%

32 HCl CEM Dynamic Spiking

33 Which LOD/LOQ/MAU/MDC? MKS Instruments 33 ASTM D6348-98/03 LOD – Measure of Precision EPA Method 320 – Max Anal Uncertainty (MAU) MDC =2 stdev at 95% CI from Residual NIOSH 3800 Method 1 - LOD (ambient) Examines Interference Residuals

34 Detection Limits - Which One? MKS Instruments 34 1 set of data

35 Compliance Software MDC/LOD/MAU/OFC EPA-M320,ASTM D6348-12 MKS Instruments 35

36 Manual Check TE-HS LOD Software Included MKS Instruments 36 CH 4 12 ppm HCl 30 ppb Goodness of Fit-2x sigma

37 Comparison of HCl Calibrations Precision MKS Instruments 37

38 Comparison of MKS FTIR Analyzers Solutions for HCl HCl DL* (30 sec) Main Components Measured Information Broadband CEM TUV Certified EPA Certified <300 ppb HCl, SO 2, NO x, CO, CO 2, H 2 O, NH 3, HF, N 2 O, CH 4, CH 2 O No LN2 needed Requires daily N2 Zero High-sensitivity HCl FTIR EPA Certified <30 ppb HCl, Formaldehyde, HF, CO, CO 2, CH 4 No LN2 needed No daily N2 Zero Uses Auto-Reference method 38 * Detection Limit based upon 3σ in 30% H2O and 25% CO


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