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

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 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

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 D )
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
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 D 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
Before Installation, instrument manufacturer must perform:
Linearity
Detection Limit
Cross Sensitivity
After Installation to Validate must perform:
RATA Test on Other than HCl compounds
Reference Method Test HCl - EPA-M321 RATA
Includes Dynamic Spike
7 day drift test
Daily and On-Going (all automated)
Zero
Dynamic Spike or Dry Cal Span (Wet or Dry)
Periodic RATA
Provide 30 day rolling avg HCl

6. Advantages of FTIR No training needed Measurements done Hot-Wet
Required for polar components HCl, HF
Works with High CO2 and H2O
No Chemical Conversions
Multiple components Simultaneously
THCs, HCl, HF, VOCs, NOx, SO2, 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)

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 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. The FT-IR Light Modulator Creating the Interferogram
HeNe Laser monochromatic light
Fixed Mirror
Beamsplitter
Moving Mirror
Optical Retardation - difference between the distance the light travels in the two arms of the pathway above. If the difference is 0 (same length of travel) there will be Constructive interference (all light passes to the detector) otherwise there is interference between the beams and less light gets to the detector.
At 1/4 wavelength displacement of the moving mirror the optical retardation is 1/2 wavelength which causes destructive interference and no light reaches the detector.
Constant velocity movement of the mirror causes a sinusoidal response seen by the detector.
Laser light is very narrow and is used to calibrate the exact positions of when the Zero crossing occur.
IR Source
To Gas Cell & Detector

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

12. Background and Sample Absorbance = - Log (I/Io) BACKGROUND (Io)
N2 Purge
SAMPLE (I)
1000 ppm NH3
Single Beam Background
N2 purging instrument then background collected (eg. is 1cm-1)
Single Beam Sample
Sample gas flowing through cell (eg. is 1000 ppm NH3 at 1cm-1)
Absorbance = - Log (I/Io)

13. Absorbance is Proportional to Concentration
Absorbance = - Log (I/Io)
Absorbance =  • C • path
FFT of Sample
1000 ppm NH3

14. FTIR Analysis Method Analytical Method
Classical Least Squares (CLS) then
Beers Law, Abs = a b c  measured spectrum
a absorptivity coefficient or ε  from calibration
b path 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 data point every 30 seconds
40 sample cell turnovers per minute
Self -validating sample method
Cement – Only acceptable reference method EPA M321

15. Classical Least Squares
Model
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
Classical Least Squares
K contains the pathlength and the molar absorptivity coefficient for each component at a particular wavelength.

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

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

18. Examples of Pre-Abatement Coal Fired (Cement Plant) Gas Concentrations Measured by FTIR
HCl
5-300
0-5
0-4
<1
2-4
SO2
0-60
0-200
0-240 0*
NOx *
~ 150
~ 800
CH2O
5-25
0-3
3-9
2-3
~ 20
~ 3
*NH3
0-150
0-40
0-80
0-50
~30
0-15 CO * * *
~ 300
CH4
~ 2
~ 5
* Also includes periodic high concentration spikes
This slide compares the measurements requirements in terms of sensitivity, accuracy, etc… for US standards and European standards.
IN the next few slides, I am going to go through how FTIR can meet all these requirements.
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
H2O and CO2 also measured with targets (cost effective)
* - Not measured with high sensitivity instrument (but can do high levels)

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

20. TÜV ranges & uncertainties MKS 2030D TE9 CEM FTIR
Gas comp.
Cert. range
Supp. range 1
Supp. range 2
ELV
U/C
U/C req.
NH3
0-10 mg/m3
0-75 mg/m3 -
10 mg/m3
6.2%
30.0% CO
0-300 mg/m3
mg/m3
50 mg/m3
7.5%
SO2
mg/m3
7.0%
15.0% NO
0-200 mg/m3
0-400 mg/m3
130 mg/m3
6.8%
NO2
0-50 mg/m3
0-100 mg/m3
mg/m3
4.1%
HCl
0-15 mg/m3
0-10 ppmv
0-90 mg/m3
8.1% HF
0-3 mg/m3
1 mg/m3
19.3%
CH4
22.5%
CO2
0-25%
3.3%
H2O
0-40%
3.4%
N2O
0-500 mg/m3
4.5%
1 ppm HCl = 1.49 mg/m3

21. FTIR Suppliers - TÜV Ranges & Uncertainties
SO2
Cert. range
Supp. range 1
Supp. range 2
Rel. U/C
MKS
0-75 mg/m3
0-300 mg/m3
mg/m3
7.0% of 50 mg/m3
Comp 1
mg/m3
9.4% of 50 mg/m3
Comp 2
10.5% of 50 mg/m3
Comp 3 -
Comp 4
11.5% of 50 mg/m3
HCl
Cert. range
Supp. range 1
Supp. range 2
Rel. U/C
MKS
0-15 mg/m3
0-90 mg/m3
0-200 mg/m3
8.1% of 10 mg/m3
Comp 1 -
12.0% of 10 mg/m3
Comp 2
0-150 mg/m3
12.2% of 10 mg/m3
Comp 3
12.8% of 10 mg/m3
Comp 4
11.4% of 10 mg/m3

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, SO2, NOx, CH4, CO, NH3, H2O, CH2O
All CEMS and RM measurements from same basic location

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

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 N2 Background → easier integration than standard FTIR – turn on and go
No Calibration Needed– “Canned” Method
Can measure HCl, CH2O, HF, H2O, N2O, CH4 with similar high sensitivity – or ELIMINATE Spectral Regions of no concern –hardware based

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

27. Detector/Hardware Influences High Sensitivity System HCl, HF, CH4, H2O, N2O, CH2O
TE9u CEM
LN2-16u MCT (77K)
TE-HS CEM
Sensitivity (signal)
<noise
>S/N
IR Band-pass Filters
spectral
region

28. EXAMPLE of No Cross Sensitivity
No change in HCl concentration
900 ppm CH4 and 6% H2O

29. Staged Blowback Filtration 80 psig

30. MKS FTIR CEM Data 15 Days 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%

31. H2O 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 H2O to < 0.5%, Filter cake sublimes to HCl gas, Conc. Inc. rapidly
Then, comes back to Steady-State when H2O > 0.5%

32. HCl CEM Dynamic Spiking

33. Which LOD/LOQ/MAU/MDC?
ASTM D /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?
1 set of data

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

36. Manual Check TE-HS LOD Software Included
Goodness of Fit-2x sigma
Manual Check TE-HS LOD Software Included
CH4 12 ppm
HCl 30 ppb

37. Comparison of HCl Calibrations Precision

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, SO2, NOx, CO, CO2, H2O, NH3, HF, N2O, CH4, CH2O
No LN2 needed
Requires daily N2 Zero
High-sensitivity HCl FTIR
<30 ppb
HCl, Formaldehyde, HF, CO, CO2, CH4
No daily N2 Zero
Uses Auto-Reference method
* Detection Limit based upon 3σ in 30% H2O and 25% CO