Pilot-Plant Performance Testing to S

D l t f EPA HCl CEDevelopmen

t o

f an EPA HCl CE

Performance Specification

Jeff Ryan

US EPA

– Offi f R h d D l 

Office o

f

Researc

h an

d

Developme

and

Peter Kariher

ARCADIS US Inc ARCADIS US, Inc

Office of Research and DevelopmentNational Risk Management Research Laboratory. 

37th Stationary Source Sampling & Analysis for Air 

March 26, 2013 

Hilton Head, SC
Background

• OAQPS is developing a new Performance 

Sp ( ecification (PS-18) pp for HCl CEMS to support emissions monitoring in the Portland Cement Mand Electric Utility MATS rules

• D t di CEM t f 

Data regarding CEMs measurement performanc

quality to inform decision making is a componenthe development process

• ORD is conducting research to support data nee• Independent, industry-driven research/demonst

t ti l t ki l testing also taking place

1
M Thi t C id Many Things 

to 

Consider ...

• HCl emissions monitoring is a new requirement w

HCl emissions monitoring is

a new requirement w

own challenges

–Multiple technologies are available with many fundament

differences and technical issues

–Movement towards a performance based Performance S

that is inclusive of these technologies

–Low level regulatory emission limits present technical ch

• HCl CEMS• Reference Methods (RMs) Reference Methods (RMs)

–Quality and availability of Reference Gas Standards–Practicality of associated procedures

2
EPA Research and Support Obje

• Establish data supporting finalization of PS• Evaluate commercial HCl CEMS (extractive only) 

D ft PS d t ll d d t ti i Draft PS un

der con

troll

e

d an

d represen

t

ative emis

environments

–Stack 

g p as com

position

–HCl emission levels

• Demonstrate suitability of candidate RMs• D t t t t d lit f il bl G S

Demons

tra

te s

t

a

tus an

d quality o

f avail

able 

Gas S

• Provide environment for vendors to optimize their 

3
Participating HCl CEMS

• 4 Commercially 4 Commercially

-available extractive technologie

available, extractive technologie

Test Program

–2 Gas Filter Correlation 

( ) GFC

)

–1 FTIR–1 Cavity Ring-Down (CRD)–No TDLAS cross stack system

• Span ranges:

–

0

-

5 ppm

–

0

-10 ppm

?

–Over span measurement capabilities ( Over span measurement capabilities

(

≤100 p

100 p

4
PS-18 Elements and ORD Testing 

• Interference Tests Interference Tests• Limit of Detection (LOD) Tests• 7-Da

y Drift

• Linearity• RATAs• Dynamic Spiking

5
Test Facility

• 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

6
Reference Methods

• Method 26A (MATS only)

–P i dt i P

aire

d

trains

–Static spiking?

• Methods 320/321 

(ASTM D6348-12 too

)

–Looking at 3 different high resolution FTIR analyzers–Focus on DLs, measurement quality and RM performance 

very low very low HCl levels

–Point of reference for HCl Gas Standards

7
Testing Status

• Still in early stages of testing due to extended faci

maintenance

• All HCl CEMSs and RM FTIRs installed

–Vendors recently p returned for final optimization

• Testing to date has focused on:

–FTIR RM measurement capabilities and performance–E l ti HCl G St d d Evaluating HCl Gas Standards

–Preliminary interference tests–Preliminary LOD tests

–Reference Method performance–All while firing on NG with HCl injection

• Target HCl stack concentrations 0.2 – 2 ppm

8
Testing ...

• We’re only now just getting started

–Mostly proof-of-concept at this time–“Learning and practicing”

• Working primarily with NG and pure gas injectio

–Some coals but Some coals, but HCl concentrations too high concentrations too high

• We’ve still managed to try a few things ...

9
Interference Testing ...

• What gases and concentrations to test?• How practical is performing the test?

1.2

• How do individual vs. combined gases compare

0.8

1

ppm)

ppm SO2

m SO2

pm

CH4

aldehyde

0 40.6

Cl Concentration (p

~700 p

~80 pp

~800 p

~750 ppm

~20 ppm Forma

0.20.4

HC

10

0

9:00:1...

9:07:5...

9:15:3...

9:23:0...

9:30:3...

9:38:0...

9:45:4...

9:53:2...

10:00:...

10:08:...

10:15:...

10:23:...

10:31:...

10:38:...

10:46:...

10:53:...

11:01:...

11:08:...

11:16:...

11:24:...

11:31:...

11:39:...

11:46:...

11:54:...

12:02:...

12:10:...

12:18:...

12:26:...

12:34:...

12:42:...

12:50:...

12:58:...

1:06:1...

1:13:5...

1:21:2...

1:28:5...

1:36:3
160

Reference FTIR with HCl and Formaldehyde

140100120

6080

entration (ppmv) 

4060

Conce

HCL at 3.9 ppmv

0

20

0 50 100 150 200 250 

11 -20

0 50 100 150 200 250 

Time (minutes)
120

HCl CEMS Response to Formaldehyde

100

80

pmv)

4060

Concentration (pp

20

HCl 

0

10:04:48 AM 11:16:48 AM 12:28:48 PM 1:40:48 PM 2:52:48 PM 

12 -20

Time (HH:MM:SS)
LOD Testing

• How well does the approach work?• What concentration(s) should be used?

H d thi h t th ?

Reference FTIR HCl CEMS "A" HCl CEMS "B" 

0.5 ppm Point avg 0.61 0.57 0.78 

std 0.03 0.02 0.01 

• How does this approach compare to others?

LOD 0.08 0.05 0.04 

2 ppm Point avg 2.00 1.99 2.61 

std 0.04 0.01 0.04 

LOD 0.12 0.04 0.12 

0.2 ppm Point avg 0.19 0.19 0.41 

std 0.02 0.01 0.04 

LOD 0.06 0.04 0.13 

SystemConfig

ASTM MDC 1 ASTM MDC 2 ASTM MDC 3 EPA M320 MAU EPA M320

FMU*R

EPA 

LN2 ‐16 0.14 0.14 0.15 0.25 0.27 0.2

13
Method 26A - How low can y

Cal Points Area Calculated Agreement y = mx+b

• Analytical

ug/mL Counts ug/mL % m = 35.41747

0.20 6.81088 0.19 ‐3.74% b = ‐7.8701E‐03

1.00 36.57592 1.03 3.29% y = area

5 00 . 178 89946 178.89946 5 05 . 1 03% . x = amount

10.00 353.41158 9.98 ‐0.21% MDL = 0.03 ug/mL

15.00 529.28789 14.94 ‐0.37%

Liquid Total Total Total

• In-stack Example

Target Functional Sample Sample Sample Sample Sample Sample Sample Sample

Conc. Dilution Conc. Volume Mass Rate Time Volume Volume Conc Conc

ug/ml Factor ug/ml mL mg cfm min ft3 m3 mg/m3 ppm

0.20 1 0.2 275.0 0.06 0.75 30 22.5 0.637 0.086 0.06

14
FTIR- How low can you go?

2.5

Dyanmic Spiking on Natural Gas

1 5

21

1.5

ncentration 

0.5

Con

0 5

0

11:30:49 AM 11:36:50 AM 11:42:50 AM 11:48:52 AM 11:54:52 AM 12:00:53 PM 12:06:54 PM 12:12:54 PM 12:18:55 PM 12:24:56 PM 12:30:56 PM 12:36:57 PM 12:42:58 PM 12:48:59 PM 12:55:00 PM

1:01:00 PM

1:07:01 PM

1:13:02 PM

1:19:03 PM

1:25:03 PM

1:31:04 PM

1:37:05 PM

1:43:06 PM

1:49:06 PM

1:55:07 PM

2:01:08 PM

2:07:08 PM

2:13:09 PM

2:19:10 PM

2:25:11 PM

2:31:12 PM

2:37:12 PM

2:43:13 PM

2:49:14 PM

2:55:15 PM

3:01:15 PM

3:07:16 PM

3:13:17 PM

15

‐0.5 111111111111111
Reference Method Agreement

M321/AST

M M-26A Absolute

Target FTIR HCl HCl Avg Difference

ppm ppmv / wet ppmv / wet ppmv / wet

0.2 0.19 0.27 0.080.5 0.59 0.58 0.012.0 1.98 2.01 0.02

16
3

Let’s Put it All Together ...

2.5

M321/ASTM M-26A

Target FTIR HCl HCl Avg HCl CEMS "A" HCl CEMS "B" HCl CEMS "C"

ppm ppmv / wet ppmv / wet ppmv / wet ppmv / wet ppmv / wet

0.2 0.19 0.27 0.19 0.41 0.35

0.5 0.59 0.58 0.57 0.78 0.70

2 0 1 98 2 01 1 99 2 61 1 95

2

(ppm)

2.0 1.98 2.01 1.99 2.61 1.95

1.5

HCl Concentration 

0.5

1 

0

:09 :39 :18 :57 :27 :09 :36 :10 :45 :24 :54 :33 :14 :42 :21 :00 :30 :09 :47 :24 :54 :33 :03 :42 :21 :58 :30 :09 :39 :18 :48 :18 :05 :36 :15 :45 :24 :54 :33 :14 :42 :21 :51 :30 :09 :399:00:

9:07:

9:15:

9:22:

9:30:

9:38:

9:45:

9:53:

10:00:

10:08:

10:15:

10:23:

10:31:

10:38:

10:46:

10:54:

11:01:

11:09:

11:15:

11:23:

11:30:

11:38:

11:46:

11:53:

12:01:

12:08:

12:16:

12:24:

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12:46:

12:54:

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13:39:

13:47:

13:55:

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14:17:

14:25:

14:33:

14:40:

17 Time
Gas Standards

• Gas Standards are needed as part of PS and on Gas Standards are needed as part of PS and on-

Quality Assurance operations

• Conventional comp g ( y), p ressed gases (dry), evaporativ

(wet), and humidification of dry gases being cons

• NIST traceable gas standards do not yet exist

(but are in the works (but are in the works – really!) really!)

• Reference Gas quality at low concentrations and 

p y racticality of use a focus of our efforts

18
Gas Standard Testing

• C dG ompresse

d

Gases:

–Ordered ~20 HCl cylinders (concentrations 

ranging from ~2-100 ppm) from Airgas and 

Airgas F

Tag Value Mea

pp

m p

Linde last Summer 

–Initial measurements 10-50% low, most ~20%

–After 6 months - some stable, some not

pp p1.84 14.60 49.28 9

47.55 46

–Good news ... 100.7 95

• Hovacal:

W h i ith

Target Hovacal 

–

We 

have many years exper C t ti Cl ltd 

ience with

the Hovacal

–Much faster response and equilibration

Concentration

C

alculate

d

HCl ppm HCl ppm 

0.5 0.57 1.0 1.15 2.0 2.24 5 0 5 50 

–We believe it to be accurate, but ...

• Bottom line is that it is critical to our research 

th t h li bl f

5.0

5.50

10.0 10.73 

19

th

a

t we 

have a reli

able re

ference gas
NIST Status

• Actively developing their capabilities to provide trac

–Prepared m ltiple ref gas c linders (8 Prepared multiple ref gas cylinders (8-12ppm)–Cylinders concentrations established and confirmed

• Electrochemical titration (U= 0.5%)• IC confirmation

–Now establishing their RGM naming system (Tiger Optics C–Expect to be able to provide RGMs with U ≤ 2%

• Future plans

–Expect to be able to name RGM cylinders for gas vendors 

several months several months

–Prepare and study low level (~2 ppm) ref gas cylinders–Inter-laboratory comparison study with VSL this Summer

20
Gas Vendor Status

• Multiple gas vendors now providing low level (<10 

gas standards gas standards

–Targeting 1-2 ppm gases

• Ver

y p

 aware of recent discre

pancies and are workin

those issues

• Improving/establishing their certification system ins• E i i t bilit Examining s

t

abilit

y

• Discussing guidance for cylinder use• Anxious to send RGM cylinders to NIST Anxious to send RGM cylinders to NIST

21
What We’ve Learned So Far ...

• I t f i t t id ti In

terferences are an impor

tan

t consideration

–Spectral and chemical

• Candidate Reference Methods are suitable for low 

Candidate Reference Methods are suitable for low 

• HCl Gas Standards are a challenge

–Need accurate and reliable point of reference/traceability – –Dry gases have transport concerns–Practicality of the wet, evaporative systems

• There s’ much work left to do much work left to do ...

22
Future Plans ... Future Plans ...

• Expect to be testing through end of CY13• F ll i l t PS Fully implement PS-18 ( lti l ti ) 18 (multiple times)

–Conduct more comprehensive Interference Tests–Conduct more comprehensive LOD Tests–RATAs on spiked NG and low HCl coal–Consider practical alternatives

• Work on Work on HCl CEMS Dynamic Spiking CEMS Dynamic Spiking

–levels, techniques, during RM measurements

• Continue to facilitate the establishment of NIST Tra• Support regulatory data needs

23
Questions ...

24