Mercury CEMS Significant Technical Issues And Recent Resultsrmb-consulting.com/papers/Hg Presentation for Utility... · 2008-09-10 · Mercury CEMS Significant Technical Issues And

© RMB Consulting & Research, Inc.

Richard McRanie Richard McRanie RMB Consulting & Research, Inc. RMB Consulting & Research, Inc.

5104 Bur Oak Circle 5104 Bur Oak Circle Raleigh, NC Raleigh, NC 919919--510510--04830483

Mercury CEMSMercury CEMSSignificant Technical IssuesSignificant Technical Issues

And Recent ResultsAnd Recent Results

EPRI Hg Measurements Workshop EPRI Hg Measurements Workshop January 24, 2007January 24, 2007


Trimble Hg CEMS Population UpdateTrimble Hg CEMS Population Update

♦♦Thermo InertialThermo Inertial♦♦Tekran InertialTekran Inertial♦♦Thermo Thermo ““Game CubeGame Cube””♦♦Tekran M&CTekran M&C♦♦Sick Sick MaihakMaihak♦♦DuconDucon♦♦OpsisOpsis


Subjects For TodaySubjects For Today

♦♦Lessons LearnedLessons Learned♦♦Regulatory IssuesRegulatory Issues♦♦IRM IssuesIRM Issues♦♦Calibration IssuesCalibration Issues


Lessons LearnedLessons Learned

If You Put Stainless In A Wet Stack,If You Put Stainless In A Wet Stack,It Will Not Be ThereIt Will Not Be ThereWhen You Return!When You Return!





Lessons LearnedLessons Learned

♦♦Loss Of Probe Heater Trips Are Loss Of Probe Heater Trips Are EssentialEssential•• Current or TemperatureCurrent or Temperature•• Otherwise, Days of Acid CleaningOtherwise, Days of Acid Cleaning

♦♦Operating Without An Oxidized Operating Without An Oxidized Calibrator Tells You NothingCalibrator Tells You Nothing

♦♦Ditch The 4Ditch The 4--20 ma Signals20 ma Signals•• Sets up an Artificial Range Sets up an Artificial Range -- BADBAD


Regulatory IssuesRegulatory Issues

♦♦Range And Span Rule Language ObsoleteRange And Span Rule Language Obsolete•• Modern Digital Analyzers DonModern Digital Analyzers Don’’t Have Rangest Have Ranges•• 44--20 ma Creates an Artificial Range20 ma Creates an Artificial Range

♦♦How Do We Handle 10/50How Do We Handle 10/50--1 Hg 1 Hg Excursions?Excursions?

♦♦There Are Alternatives If One There Are Alternatives If One Understands How Hg CEMS And Understands How Hg CEMS And Calibrators Work Calibrators Work

0

5

10

15

20

25

30

35

40

11/22/2006 11/23/2006 11/24/2006 11/25/2006 11/26/2006 11/27/2006 11/28/2006 11/29/2006 11/30/2006 12/1/2006

Day

Hg

Co

nce

ntr

atio

n (

ug

/m3 )

Thermo 80i Stack Gas Responses Thermo 90iB Stack Gas Response

Example Hg Analyzer/System Calibration

0

1

2

3

4

5

6

7

8

9

10

0 1 2 3 4 5 6 7 8 9 10

Hg, µg/m3

Hg

, µg

/m3



Range And SpanRange And Span

♦♦Experiments Are Being Conducted To Experiments Are Being Conducted To Illustrate The Wide Range Capability Illustrate The Wide Range Capability Of Hg CEMSOf Hg CEMS

♦♦Initial Experiments Are Very Initial Experiments Are Very EncouragingEncouraging


Regulatory Issues IIRegulatory Issues II

♦♦NIST Traceable Elemental & NIST Traceable Elemental & Oxidized Hg StandardsOxidized Hg Standards

♦♦Traceable Elemental Calibrators Traceable Elemental Calibrators Promised By Sept 2006Promised By Sept 2006

♦♦No Vendor Has Even OneNo Vendor Has Even One♦♦No Traceability ProtocolNo Traceability Protocol♦♦Little Oxidized Work DoneLittle Oxidized Work Done

NIST

Vendor AMaster

Calibrator

UtilityCalibrator 1

UtilityCalibrator 2

Vendor BMaster

Calibrator

UtilityCalibrator 1

UtilityCalibrator 2

ExternalVerify


IRM IRM IsssuesIsssues

♦♦Conceptual IRM Is Very ComplexConceptual IRM Is Very Complex♦♦Equipment Is Very ExpensiveEquipment Is Very Expensive

•• ~$200,000~$200,000

♦♦Extremely Time ConsumingExtremely Time Consuming•• 33--4 Days Minimum 4 Days Minimum

♦♦Are All The Requirements Necessary?Are All The Requirements Necessary?


IRM Requirements IIRM Requirements I

♦♦33--Point Elemental CalibrationPoint Elemental Calibration•• 2% of span or 2% of span or ±±0.2 0.2 µµg/mg/m33 criteriacriteria

♦♦33--Point Oxidized CalibrationPoint Oxidized Calibration•• 5% of span or 5% of span or ±±0.5 0.5 µµg/mg/m33 criteriacriteria

♦♦PrePre--test Dynamic Spike test Dynamic Spike –– 2 levels, 3 runs2 levels, 3 runs•• 100 100 ±±5% Recovery plus 5% Recovery plus ==5% RSD, or if either 5% RSD, or if either

failed, alternatively failed, alternatively ==0.2 0.2 µµg/m3 difference g/m3 difference between theoretical and actual spike between theoretical and actual spike


IRM Requirements IIIRM Requirements II

♦♦Make Sample RunsMake Sample Runs•• Nominally 30Nominally 30--Minutes Each RunMinutes Each Run

♦♦Single Level System Integrity TestSingle Level System Integrity Test•• Minimum of every 4 runsMinimum of every 4 runs•• 5% of span or 5% of span or ±±0.5 0.5 µµg/mg/m33 criteriacriteria

♦♦PostPost--test Dynamic Spike, 2 levels, 3 runstest Dynamic Spike, 2 levels, 3 runs•• 100 100 ±±10% Recovery plus 10% Recovery plus ==5% RSD, or if either 5% RSD, or if either

failed, alternatively failed, alternatively ==0.2 0.2 µµg/mg/m33 difference difference between theoretical and actual spikebetween theoretical and actual spike


IRM Tests At TrimbleIRM Tests At Trimble

♦♦InstalledInstalled Tekran Used As IRMTekran Used As IRM♦♦Was Used To Evaluate Was Used To Evaluate

Calibration/Spiking RequirementsCalibration/Spiking Requirements♦♦Also Used To Conduct Also Used To Conduct RATAsRATAs On On

Two Two InstalledInstalled Thermos and PSA/GEThermos and PSA/GE♦♦5050--foot Sample Linesfoot Sample Lines


Trimble IRM ResultsTrimble IRM Results

♦♦All Pre and Post IRM Calibration And All Pre and Post IRM Calibration And Spiking Tests With Tekran Passed Spiking Tests With Tekran Passed IRM SpecificationsIRM Specifications

♦♦Both Thermos and PSA/GE Passed Both Thermos and PSA/GE Passed RATA Requirement of RATA Requirement of ±±1.0 1.0 µµg/mg/m33 Of Of The Mean Reference Method ValueThe Mean Reference Method Value


IRM Tests At YatesIRM Tests At Yates

♦♦InstalledInstalled Thermo Used To Conduct Thermo Used To Conduct IRMIRM•• Custom Built Thermo Probe Designed For Custom Built Thermo Probe Designed For

Spiking Spiking –– No Cost, Thanks ThermoNo Cost, Thanks Thermo

♦♦Used To Conduct RATA On Used To Conduct RATA On InstalledInstalledTekranTekran

♦♦200200--ft Sample Linesft Sample Lines♦♦Ontario Hydro And Carbon Traps Also Ontario Hydro And Carbon Traps Also

Done Done


Yates IRM ResultsYates IRM Results

♦♦PrePre--test Calibration and Dynamic test Calibration and Dynamic Spikes Completed With DifficultySpikes Completed With Difficulty•• Miscellaneous Problems and Varying Stack Miscellaneous Problems and Varying Stack

ConcentrationConcentration

♦♦Only 5 IRM Runs Completed Only 5 IRM Runs Completed –– Only 3 Only 3 Met IRM SpecificationsMet IRM Specifications

♦♦HovaquickHovaquick Zapped By Static DischargeZapped By Static Discharge


Yates RA ResultsYates RA Results

0.740.7430.430.4App KApp K

0.070.0714.014.0ThermoThermo

0.080.0810.810.8TekranTekran

RelRel DiffDiff((µµg/mg/m33))

RelRel AccuracyAccuracy(%)(%)

AnalyzerAnalyzer


IRM IRM -- What Can Be Eliminated?What Can Be Eliminated?

♦♦Pretest Elemental CalibrationPretest Elemental Calibration•• Not Needed In Addition To Oxidized CalibrationNot Needed In Addition To Oxidized Calibration

♦♦All Spiking All Spiking –– Only Adds Time And CostOnly Adds Time And Cost•• Not Telling Us Anything Except That The Not Telling Us Anything Except That The

Spiking Equipment Did Not Work Or That The Spiking Equipment Did Not Work Or That The Stack Hg Concentration Had ChangedStack Hg Concentration Had Changed

•• There Has Never Been Any Evidence Of Stack There Has Never Been Any Evidence Of Stack Matrix Or Spectral Interference Matrix Or Spectral Interference


Calibration ProblemsCalibration Problems

♦♦Daily/Weekly QA/QC Checks Have Been Daily/Weekly QA/QC Checks Have Been Unreliable Unreliable –– Frequent FailuresFrequent Failures

♦♦Consistent Difference in Dry HgConsistent Difference in Dry Hg00 and Wet and Wet HgHg+2+2 Calibration ChecksCalibration Checks•• Changed From DayChanged From Day--to Dayto Day•• Delta Increased Over TimeDelta Increased Over Time

♦♦Experiments Were Designed To Evaluate Experiments Were Designed To Evaluate The Calibration ProblemThe Calibration Problem

Elemental Hg Calibrator

HovaquickNitr

ogen

DI H

2O

Vap

oriz

er

Air MFC (lpm)

Liquid MFC

(g/min)

Iner

tial F

ilter~10 lpm

5 lpm

~15 lpm

Inertial Probe

Calibration Actuator Valve

Dilution Orifice

Stack Gas

Hg Monitor

Response Elemental Calibration Gas - System A

5.0

5.5

6.0

6.5

7.0

7.5

8.0

0 1 2 3 4 5 6 7 8 9 10 11 12 13

Calibration Injection

Ele

men

tal H

g (

ug

/scm

)

Dry Elemental Wet ElementalRefernce Concentration Corrected Dry ElementalCorrected Wet Elemental

3.5 % H2O

6.9 % H2O 10.4 % H2O

3.5 % H2O 7.2 % H2O 10.6 % H2O

Response Elemental Calibration Gas - System B

8.0

8.5

9.0

9.5

10.0

10.5

11.0

11.5

12.0

12.5

13.0

0 1 2 3 4 5 6 7 8

Calibration Injection

Ele

men

tal H

g (u

g/s

cm)

Dry Elemental Wet ElementalRefernce Concentration Corrected Dry ElementalCorrected Wet Elemental

5.1 % H2O 10.1 % H2O

15.0 % H2O


Elemental Calibration Elemental Calibration –– Bottom LineBottom Line

♦♦Dry Elemental Calibration Is Not Dry Elemental Calibration Is Not Quantitative On Inertial ProbesQuantitative On Inertial Probes

♦♦Need To Add 7Need To Add 7--10% Moisture10% Moisture♦♦Need To Correct Dilution Ratio Need To Correct Dilution Ratio

For Wet CalibrationFor Wet Calibration♦♦Additional Experiments are Additional Experiments are

Planned For NonPlanned For Non--Inertial Probes Inertial Probes

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Mercury CEMS Significant Technical Issues And Recent Resultsrmb-consulting.com/papers/Hg Presentation for Utility... · 2008-09-10 · Mercury CEMS Significant Technical Issues And