determining the variability of continuous mercury monitors ...€¦ · eerc . . . the international...

Determining the Variability of Continuous Mercury Monitors (CMMs) at

Low Mercury Concentrations

EUEC 2011 Phoenix , Arizona

January 31 – February 2, 2011

Dennis Laudal

EERC . . . The International Center for Applied Energy Technology

Tekran Comments

• This presentation is the original except for the following. • Slide 10 – the probe labels were corrected • Slide 15 – The correct R and R2 values are provided • Other corrections for the EERC Research Report on the ICCI

website can be found at http://www.tekran.com/wp-content/uploads/2011/06/CMM-results-at-low-Hg-Conc.pdf

http://www.tekran.com/wp-content/uploads/2011/06/CMM-results-at-low-Hg-Conc.pdf

http://www.tekran.com/wp-content/uploads/2011/06/CMM-results-at-low-Hg-Conc.pdf


Program Partners

• Illinois Clean Coal Institute (ICCI) – Dr. Francois Botha

• Electric Power Research Institute (EPRI) – Mr. Charles Dene

• U.S. Department of Energy National Energy Technology Laboratory (DOE NETL) – Mr. I. Andrew Aurelio

• Center for Air Toxic Metals® (CATM®) Affiliates Program – Mr. John Pavlish

• ThermoFisher Scientific – Mr. Jeff Socha

• Tekran Instruments – Mr. Karl Wilber

• OhioLumex – Mr. Joseph Siperstein


Project Drivers

• U.S. Environmental Protection Agency (EPA) Maximum Achievable Control Technology (MACT) Regulations – To meet regulations may require Hg control <1.0 µg/m3. Compliance verification cannot be effected without accurate and traceable low-level Hg measurements.

• Hg Abatement System Control – Accurate low-level Hg measurements are required to economically operate Hg reduction systems.

• Optimization of Coal Supply and Blending Strategies ‒ Will rely on accurate low-level Hg measurements (market acceptance of coal-fired plants may require measurement validation).

• Hg Abatement Research ‒ Low-level Hg measurements are required to properly assess new control technology performance.


Project Objectives

The primary goal of the project is to determine the actual variability of CMMs at mercury concentrations <1.0 µg/Nm3.

• Determine the variability of the components of the mercury-spiking systems.

• Determine the zero-mercury concentration for the instruments.

• Based on “true” spiking values for Hg0 and HgCl2, determine the variability of the CMMs over a 4-hour time frame for three different mercury concentrations.


• Compare the variability of carbon trap measurements using the OhioLumex and modified EPA Method 1631.

• Compare the variability results with and without acid gases (SO2 and HCl) added to the flue gas.

• Determine the performance of the CMMs measuring low levels of mercury (<1.0 µg/Nm3) when firing coal.

Project Objectives


• Task 1 – Design and build mercury-spiking systems and ensure all equipment is operating at the highest level.

• Task 2 – Complete test plan firing natural gas (2-week-long pilot-scale tests).

• Task 3 – Complete test plan firing an Illinois (Knighthawk) bituminous coal.

Project Tasks


Mercury Measurement Methods

• CMMs

‒ Tekran Model 3300

‒ ThermoScientific Freedom System

– Sorbent trap method (EPA Method 30B), with traps to be supplied by OhioLumex

‒ Directly analyzed using the OhioLumex RA-915+ mercury analyzer with PYRO-915 attachment

‒ Analyzed by Frontier Geosciences using modified EPA Method 1631


Tekran

ThermoScientific


Test Plan for Natural Gas Tests

Test Condition

Mercury

Mercury Concentration, µg/Nm3

– Blank 0 1 Hg0 0.25 2 Hg0 0.5 3 Hg0 1.0 4 HgCl2 0.25 5 HgCl2 0.5 6 HgCl2 1.0 7 Hg0 and HgCl2 0.25/0.25


Test Plan for Coal Test Pilot-Scale Test Firing a Knight Hawk Illinois Coal

System Configuration:

Boiler ESP Wet FGD Baghouse


Baseline Mercury Concentration Firing PTC on Natural Gas

Sample 1 Sample 2 Date

Time Sampled,

min

Hg on Trap,

ng

Measured Hg Conc., µg/Nm3

Hg on Trap,

ng

Measured Hg Conc., µg/Nm3

2/15/10 180 12.0 0.033 12.1 0.034 4/26/10 240 19.3 0.033 19.3 0.033

4/27/10 240 13.9 0.024 14.7 0.024

4/28/10 240 16.0 0.022 14.0 0.021

4/29/10 240 8.9 0.014 10.6 0.015

5/24/10 240 35.4 0.088 44.7 0.085

5/25/10 240 17.6 0.037 15.2 0.035

5/26/10 240 12.2 0.025 11.1 0.025

5/27/10 240 9.9 0.021 10.2 0.021

Ambient Air Background Hg = 12 ng/m3 (0.012 µg/Nm3)


Summary of Overall Results

Sorbent Trap Data, µg/Nm3 on a wet basis

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

Tek

ran

Res

ults

, µ

g/N

m3 o

n a

wet

bas

is0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

Natural Gas - No SO2 and HClNatural Gas - with SO2 and HClIllinois Coal

R2 = 0.995

Sorbent Trap Data, µg/Nm3 on a wet basis

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2

Therm

o R

esu

lts,

µg/N

m3 o

n a

wet

basi

s

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

Natural Gas - No SO2 and HClNatural Gas - with SO2 and HClIllinois Coal

R2 = 0.863

Graph Error: Thermo R=0.863 and R2=0.745 Tekran R=0.995 and R2=0.990


• Overall, the testing went well.

• The baseline mercury levels when firing natural gas were very low (at or near ambient mercury levels).

• Both the Tekran and Thermo CMMs worked well on natural gas with and without the addition of the acid gases.

• The Tekran has a lower detection limit than the Thermo system, although both were challenged during the baseline conditions (no mercury added).

• The quadtrain sorbent trap results for all the tests provided a high level of precision.

General Observations


• The calibrators used for both instruments was consistent and within 10% of the stated value.

• The Tekran has a lower detection limit than the Thermo system, although both were challenged during the baseline conditions (no mercury added).

• Although there was some variability in the mercury emissions, the mercury concentrations were consistent over the time each quadtrain sorbent trap sample was taken.

• When firing coal, the Tekran appeared to match the sorbent results, but the Thermo system did not perform as well as expected.

General Observations


• ThermoScientific believes they have determined the problem and are planning a repeat test under Subtask 4.10.

• Testing to evaluate the effects of bromine addition when measuring low-level mercury concentrations. This project has the same partners except the Wyoming Clean Coal Program rather than ICCI.

Future Testing


Disclaimer

This presentation was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government, nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

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