EUEC 2015 Experience using Cavity Enhanced Absorption Spectroscopy (CEAS) for HCl measurement on a coal-fired power plant

Transcription

1 Steve Gibbons, Business Development - CEMS EUEC 2015 Experience using Cavity Enhanced Absorption Spectroscopy (CEAS) for HCl measurement on a coal-fired power plant

2 Introduction Steve Gibbons Business Development Manager CEMS ABB Inc. (Measurement & Analytics) Tel: +1 (215) Agenda Current status of PS-18 / Procedure 6 Recap of available HCl measuring technologies Off-Axis ICOS technology Practical Demonstrations Conclusions

3 PS-18 / Procedure 6 Current Status Proposed Rule published on May 14, 2014 (79 FR 27690) Commenting period extended to July 13, 2014 Total of 17 comments submitted by various stakeholders Rule expected to be published in Feb/Mar 2015 MATS compliance deadline April 16, 2015 Key Issues Paired reference method trains Accuracy of reference methods Impractical field certification e.g. interference, LOD, linearity Availability of low level NIST traceable HCl cylinders Methods and frequency of system validation

4 We re hanging in there Pioneers of HCl CEMS in the U.S. CEMS market?! there s always PS-15! (ABB also pioneered FTIR based CEMS in 1993)

5 HCl Monitoring Three Main Technologies TDLAS Tunable Diode Laser Absorption Spectroscopy Laser (Coherent Light) Optical Path Length 3-40 feet (depending on stack diameter) Detector Single or Dual Pass FTIR Fourier Transform InfraRed IR Source (Incoherent Light) Optical Path Length feet Detector Multi-Pass Cell CEAS Cavity Enhanced Absorption Spectroscopy Laser (Coherent Light) Optical Path Length Up to 12 miles or longer! Detector Optical Cavity with highly reflective mirrors

6 Los Gatos Research Pioneer and world leader in laser-based gas sensing

7 ABB s solution: Off-Axis ICOS High resolution absorption with long path lengths Optical cavity provides long effective pathlength (up to 20 miles or longer) High sensitivity allows for detection of very weak absorptions (ppb/ppt concentrations) Chemometrics enables quantification of multiple gases in complex mixtures Very robust exact alignment, gas pressure, gas temperature are not critical Setup for LGR s patented Off-Axis ICOS technique Mirrors may be cleaned anywhere by anyone Off-Axis ICOS can be employed at any wavelength from UV through mid-ir Simple to couple multiple lasers into a single cavity for multi-species detection

8 Visualization of spectra real-time Powerful diagnostics tool H 2 O HCl

9 Off-Axis ICOS for CEMS Benefits that stack up Combination of HCl and H 2 O gives added confidence usually clear if H 2 O values are feasible Possible to combine HCl, NH 3 and H 2 O in one analyzer Potentially compatible with dilution systems up to 150:1 Visualization of spectra very powerful diagnostic tool For most applications, analyzer requires no calibration Optical cavity can be serviced on-site with minimal training, ensuring maximum availability ABB Group 2/25/2015 Slide 9

10 Sounds nice Can you prove it?

11 Practical Demonstration - 1 Coal-fired power plant combined with Hg CEMS Thanks to our partner for managing this trial Plant planning to switch to PRB* coal to achieve MATS limit emissions currently around 50ppm Hg CEMS with 35:1 dilution 25ft sample line (PTFE tubing) Plant issues restricted opportunities to optimize system design ABB Group 25-Feb-15 Slide 11 * Powder River Basin

12 Practical Demonstration - 1 Flow Diagram 25 ft (4-5 lpm) 158 o F 35:1 ratio 7 ft ¼ unheated PTFE line (0.5 lpm)

13 2-Jul-14 2-Jul-14 2-Jul-14 2-Jul-14 2-Jul-14 2-Jul-14 2-Jul-14 2-Jul-14 3-Jul-14 3-Jul-14 3-Jul-14 3-Jul-14 3-Jul-14 3-Jul-14 3-Jul-14 3-Jul-14 4-Jul-14 4-Jul-14 4-Jul-14 4-Jul-14 4-Jul-14 4-Jul-14 4-Jul-14 4-Jul-14 5-Jul-14 5-Jul-14 5-Jul-14 5-Jul-14 5-Jul-14 5-Jul-14 5-Jul-14 5-Jul-14 6-Jul-14 6-Jul-14 6-Jul-14 6-Jul-14 6-Jul-14 6-Jul-14 6-Jul-14 6-Jul-14 7-Jul-14 7-Jul-14 7-Jul-14 7-Jul-14 7-Jul-14 7-Jul-14 Load (MW) Concentation (PPM) Practical Demonstration - 1 Limited data, trends well with plant load 160 Offline for calibration checks LOAD MW Value HCL PPM Value

14 What did we learn? Not a lot, but still valuable Trial successfully proved compatibility with Hg CEMS In this case, LGR analyzer shared probe and sample line with Hg CEMS Trended well with plant load and returned to zero when plant offline No chance to demonstrate measurement ability 1ppm HCl ABB Group 25-Feb-15 Slide 14

15 Practical Demonstration - 2 Coal-fired power plant dilution-extractive CEMS ABB supplied analyzer for testing at one of largest U.S. coal-fired power plants over 4 weeks (completed Aug-2014) 100:1 dilution-extractive CEMS CR coated SP2000 M&C probe with ceramic filter 100ft sample line (frost-protected) Analyzer run in parallel to similar CRDS analyzer Note: 100:1 dilution = 10ppb (all field data presented in ppm/vol%) Thanks to our partner for managing this trial ABB Group 25-Feb-15 Slide 15

16 08/05/14 10:37:36 08/05/14 10:38:35 08/05/14 10:39:38 08/05/14 10:40:45 08/05/14 10:41:42 08/05/14 10:42:37 08/05/14 10:46:28 08/05/14 11:12:30 08/05/14 11:57:23 08/05/14 12:35:37 08/05/14 13:19:52 08/05/14 13:34:12 08/05/14 13:35:08 08/05/14 13:36:03 08/05/14 13:36:59 08/05/14 13:37:55 08/05/14 13:38:51 08/05/14 13:39:47 08/05/14 13:40:42 08/05/14 13:41:38 08/05/14 13:42:33 08/05/14 13:43:29 08/05/14 13:44:25 08/05/14 13:45:21 08/05/14 13:46:17 08/05/14 13:47:13 08/05/14 13:48:09 08/05/14 13:49:04 08/05/14 13:50:00 08/05/14 13:50:55 08/05/14 13:51:51 08/05/14 13:52:47 08/05/14 13:53:42 08/05/14 13:54:38 08/05/14 13:55:33 08/05/14 13:56:28 08/05/14 13:57:25 08/05/14 13:58:20 08/05/14 13:59:15 08/05/14 14:00:11 08/05/14 14:01:06 08/05/14 14:02:02 08/05/14 14:02:58 08/05/14 14:03:54 08/05/14 14:04:49 08/05/14 14:05:45 08/05/14 14:06:40 08/05/14 14:07:36 08/05/14 14:08:32 08/05/14 14:09:28 08/05/14 14:10:24 08/05/14 14:11:20 08/05/14 14:12:16 08/05/14 14:13:12 08/05/14 14:14:07 08/05/14 14:57:28 HCL_ppm H2O_vol% Initial zero & span (from shelter) 4 hour time period Sine wave effect is system related as can be seen in later slides. Moisture readings also very erratic during these tests indicating sampling issues. High of 8.8ppm after 2 hours Start span (9.28ppm HCl) Start zero HCL_ppm H2O_vol%

17 08/05/14 14:30:05 08/05/14 14:33:26 08/05/14 14:36:46 08/05/14 14:40:07 08/05/14 14:43:27 08/05/14 14:46:48 08/05/14 14:50:09 08/05/14 14:53:29 08/05/14 14:56:50 08/05/14 15:00:10 08/05/14 15:03:31 08/05/14 15:06:51 08/05/14 15:10:12 08/05/14 15:13:32 08/05/14 15:16:53 08/05/14 15:20:13 08/05/14 15:23:34 08/05/14 15:26:55 08/05/14 15:30:15 08/05/14 15:33:36 08/05/14 15:36:56 08/05/14 15:40:17 08/05/14 15:43:38 08/05/14 15:46:58 08/05/14 15:50:19 08/05/14 15:53:40 08/05/14 15:57:00 08/05/14 16:00:21 08/05/14 16:03:43 08/05/14 16:07:03 08/05/14 16:10:24 08/05/14 16:13:45 08/05/14 16:17:05 08/05/14 16:20:26 08/05/14 16:23:46 08/05/14 16:27:07 08/05/14 16:30:28 08/05/14 16:33:48 08/05/14 16:37:09 08/05/14 16:40:30 08/05/14 16:43:50 08/05/14 16:47:11 08/05/14 16:50:32 08/05/14 16:53:52 08/05/14 16:57:13 08/05/14 17:00:33 08/05/14 17:03:54 08/05/14 17:07:15 08/05/14 17:10:35 08/05/14 17:13:56 08/05/14 17:17:16 08/05/14 17:20:37 08/05/14 17:23:58 08/05/14 17:27:18 08/05/14 17:30:39 08/05/14 17:34:00 HCL_ppm H2O_vol% Zero & span probe) 3 hour time period Switch to zero shelter Span probe (9.6ppm) Flowed gas for 2 hours, exceeded 9.6ppm but never really stabilized Reached 1.2ppm in 10 mins, then 0.86ppm after 40 mins Moisture readings more stable, but sine wave effect still present HCL_ppm H2O_vol%

18 08/06/14 08:29:08 08/06/14 08:37:15 08/06/14 08:45:22 08/06/14 08:53:29 08/06/14 09:01:36 08/06/14 09:09:43 08/06/14 09:17:51 08/06/14 09:25:58 08/06/14 09:34:05 08/06/14 09:42:12 08/06/14 09:53:20 08/06/14 10:03:09 08/06/14 10:11:16 08/06/14 10:19:23 08/06/14 10:27:31 08/06/14 10:35:38 08/06/14 10:43:45 08/06/14 10:51:52 08/06/14 10:59:59 08/06/14 11:08:06 08/06/14 11:16:13 08/06/14 11:24:20 08/06/14 11:32:27 08/06/14 11:40:34 08/06/14 11:48:41 08/06/14 11:56:48 08/06/14 12:04:55 08/06/14 12:13:02 08/06/14 12:21:09 08/06/14 12:29:16 08/06/14 12:37:23 08/06/14 12:45:30 08/06/14 12:53:37 08/06/14 13:01:44 08/06/14 13:09:51 08/06/14 13:17:58 08/06/14 13:26:05 08/06/14 13:34:12 08/06/14 13:42:19 08/06/14 13:52:05 08/06/14 14:00:12 08/06/14 14:08:19 08/06/14 14:16:26 08/06/14 14:24:52 08/06/14 14:32:59 08/06/14 14:41:06 08/06/14 14:49:13 08/06/14 14:57:20 08/06/14 15:05:27 08/06/14 15:13:34 08/06/14 15:21:41 08/06/14 15:29:48 08/06/14 15:37:55 08/06/14 15:46:02 08/06/14 15:54:09 08/06/14 16:02:16 HCL_ppm H2O_vol% Zero & span (local) 8 hour time period Note: CR coated filter from previous HCl trial installed before testing started Switch to zero gas (local) Original ceramic filter re-installed response time improved After initial 40ppm spike, system came down to 9ppm over next 150 minutes Eductor wasn t working correctly - installed pump to pull sample from eductor bypass sine wave effect eliminated Stop zero Moisture recovers, no HCl present Span probe (9.6ppm) sluggish response Stop span gas Response time improved dramatically - 9ppm to 4ppm in 20 mins HCL_ppm H2O_vol%

19 08/07/14 09:15:01 08/07/14 09:22:49 08/07/14 09:30:37 08/07/14 09:38:25 08/07/14 09:46:13 08/07/14 09:54:01 08/07/14 10:01:49 08/07/14 10:09:38 08/07/14 10:17:26 08/07/14 10:25:14 08/07/14 10:33:02 08/07/14 10:40:50 08/07/14 10:48:38 08/07/14 10:56:26 08/07/14 11:04:14 08/07/14 11:12:02 08/07/14 11:19:50 08/07/14 11:27:38 08/07/14 11:35:26 08/07/14 11:43:23 08/07/14 11:51:11 08/07/14 11:58:59 08/07/14 12:06:47 08/07/14 12:14:35 08/07/14 12:22:23 08/07/14 12:30:11 08/07/14 12:37:59 08/07/14 12:45:47 08/07/14 12:53:45 08/07/14 13:01:33 08/07/14 13:09:30 08/07/14 13:17:28 08/07/14 13:25:16 08/07/14 13:33:04 08/07/14 13:40:52 08/07/14 13:48:40 08/07/14 13:56:28 08/07/14 14:04:16 08/07/14 14:12:04 08/07/14 14:19:52 08/07/14 14:27:40 08/07/14 14:35:28 08/07/14 14:43:16 08/07/14 14:51:04 08/07/14 14:58:52 08/07/14 15:06:40 08/07/14 15:14:28 08/07/14 15:22:16 08/07/14 15:30:03 08/07/14 15:37:51 08/07/14 15:45:39 08/07/14 15:53:27 08/07/14 16:01:15 08/07/14 16:09:03 08/07/14 16:16:52 08/07/14 16:24:39 HCL_ppm H2O_vol% HovaQuick probe 8 hour time period <20min stable at 2ppm, increased to 4.5ppm Peaked at 5ppm, H2O reading higher than 13.5% HovaQuick peristaltic pump tube damaged Reached almost exactly 4.5ppm in <15 min; H2O reading still high but closer to expected levels HovaQuick issues again ppm 10% H2O 5lpm - stabilized around 0.5ppm ppm 10% 5lpm ~20min to 0.8ppm, +10min to 0.6ppm 4.5ppm 10% 5lpm HCL_ppm H2O_vol%

20 08/09/14 10:06:15 08/09/14 10:46:50 08/09/14 11:27:25 08/09/14 12:08:00 08/09/14 12:48:35 08/09/14 13:29:10 08/09/14 14:09:45 08/09/14 14:50:20 08/09/14 15:30:55 08/09/14 16:11:30 08/09/14 16:52:05 08/09/14 17:32:40 08/09/14 18:13:15 08/09/14 18:53:51 08/09/14 19:34:26 08/09/14 20:15:01 08/09/14 20:55:36 08/09/14 21:36:11 08/09/14 22:16:46 08/09/14 22:57:21 08/09/14 23:37:56 08/10/14 00:18:31 08/10/14 00:59:06 08/10/14 01:39:41 08/10/14 02:20:16 08/10/14 03:00:51 08/10/14 03:41:26 08/10/14 04:22:02 08/10/14 05:02:37 08/10/14 05:43:12 08/10/14 06:23:47 08/10/14 07:04:22 08/10/14 07:44:57 08/10/14 08:25:32 08/10/14 09:06:07 08/10/14 09:46:42 HCL_ppm H2O_vol% Sampling stack gas throughout day 24 hours Unclear what caused these elevated concentrations, but encouraging that analyzer detected them (2ppm HCl, 60vol% H2O) HCL_ppm H2O_vol%

21 What did we learn from all this? Much more than we intended, but not everything! Proved accurate and reliable measurement at 1ppm HCl Demonstrated compatibility with 100:1 dilution system Optimizing response time of system using glass coated or chemically treated materials makes sense, but unless analyzer is installed close to sample probe, injecting dry test gas into the system on daily basis makes little sense Shown that 95% step change in under 15 min. can very likely be achieved using vaporized liquid standards (i.e. HovaCal) Illustrated importance of H 2 O to validate HCl measurement Speed and accuracy of ABB Off-Axis ICOS analyzer is extraordinary considering no field calibration was performed ABB Group 25-Feb-15 Slide 21

22 Some additional comments The sensitivity of these analyzers enabled the customer to quickly identify that there was a problem in the sample handling. Slower, less sensitive instruments (e.g. FTIR, photometers, CLD) would have greater difficulty reaching these conclusions (with a dilution setup). Doug Baer, PhD President, Los Gatos Research He was very upbeat about how well it is doing and getting the moisture channel appears to be a huge plus. They all rave about the instrument and I have little doubt the LGR instrument will be the one they order. Reggie Davis President, Spectrum Systems

23 Practical Demonstration - 3 In-house testing combined with Hg CEMS Conclusions ABB analyzer plumbed into Hg CEMS for in-house testing Thermo Fast Loop probe and Mercury Freedom System Dilution ratio 40:1 Establish optimum system design; evaluate against PS-18 <0.15ppm combined interference when challenged with other gases Hg CEMS probe compatible, independent sample line recommended Sample line material not critical when over short lengths (<30ft) Tested flow rate behind 80i Hg analyzer is 0.25 lpm (standard design) which is insufficient to share pump with ABB analyzer Thanks again to our partner

24 Interference Test

25 Conclusions We re getting close! Off-Axis ICOS demonstrated ability to measure <1ppm HCl Off-Axis ICOS compatible with 100:1 dilution-extractive CEMS Off-Axis ICOS compatible with Hg CEMS (35-45:1) H 2 O measurement of high importance to validate HCl readings Off-Axis ICOS shows <0.15ppm combined interferences (PS-18) Recommended to install independent sample line (and pump) Silconert coated stainless steel if sample line >30ft Impractical to inject dry test gas daily due to characteristics of HCl (i.e. excessive recovery time) not at all analyzer related Shown that 95% step change in under 15 min. can very likely be achieved using vaporized liquid standards (i.e. HovaCal) Reasonable changes to PS-18 / Procedure 6 critical to successful deployment of HCl CEMS technology

26 ABB Measurement & Analytics Pioneers in Continuous Emission Monitoring Pioneers of NDIR analyzers in 1952 URAS licensed from BASF to Hartmann & Braun Pioneers of FTIR based CEMS in 1993 now 4 th generation with >1,500 installations Pioneers of Cavity Enhanced Absorption Powerful and patented Off-Axis ICOS technology Pioneers of modular analyzer systems Simplifying system integration since 1996 Pioneers of gas-filled calibration cells 40 CFR 60 compliant 30,000 installed (20 yrs)

27 Thank you

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