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Mercury Mercury Control Technology Development in the Control Technology Development in the
Laboratory: International HgCEM Research and Laboratory: International HgCEM Research and
Development Development ApplicationsApplications
presented by presented by Eric M. PrestboEric M. Prestbo, Karl R. Wilber, Gabriel D. Eiras and Kai Zhang, Karl R. Wilber, Gabriel D. Eiras and Kai Zhang
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CEM ConferenceCEM Conference
MayMay--20142014, , Istanbul TurkeyIstanbul Turkey
BRIEF SYNOPSIS OF ADVANCES IN BRIEF SYNOPSIS OF ADVANCES IN
CEMCEM--BASED MERCURY FLUE GAS BASED MERCURY FLUE GAS
MEASUREMENTS, STIMULATED BY MEASUREMENTS, STIMULATED BY
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-- USA REGULATIONS USA REGULATIONS
-- PERFORMANCE EVALUATIONS IN PERFORMANCE EVALUATIONS IN
THE FIELDTHE FIELD
-- TECHNICAL ADVANCESTECHNICAL ADVANCES
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U.S. EPA EGU MATS and Cement MACTU.S. EPA EGU MATS and Cement MACT
U.S. EPA
Regulation
Existing
Source
Standard
New Source
Standard
Deadline for
Compliance
Electric Generator
Unit MATS
1.2 lbs./T-BTU 0.35 lbs./T-BTU April 2015
Portland Cement
MACT
55 lbs./MM tons
clinker
21 lbs./MM tons
clinker
September 2015
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� Summary – for EGUs, mercury concentration must be really low at ~ 170 parts per trillion (v/v) = 1.5 µg/m3 for EGUs
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MACT clinker clinker
�� Because U.S EPA Regulations are based on Because U.S EPA Regulations are based on
performance standards, there is no need to have performance standards, there is no need to have
an equivalent MCERTS or TUV certification an equivalent MCERTS or TUV certification
required in the USA for HgCEM equipment. required in the USA for HgCEM equipment.
In the USA, HgCEM Equipment Trials in In the USA, HgCEM Equipment Trials in
Real Flue Gas Determines AcceptanceReal Flue Gas Determines Acceptance
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Instead there are:Instead there are:
•• EPA Field Trials in 2004EPA Field Trials in 2004--20052005
•• Independent Research Group Performance Testing Independent Research Group Performance Testing
(i.e. EERC)(i.e. EERC)
•• Field Trials by Power and Cement CompaniesField Trials by Power and Cement Companies
•• Frequent Relative Accuracy Tests (RATA)Frequent Relative Accuracy Tests (RATA)
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U.S. EPA Trials U.S. EPA Trials 2005 2005 -- SummarySummary
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�� Relative Accuracy must be <20%Relative Accuracy must be <20%
�� Most HgCEMs did poorly, except Tekran and Thermo. Only Most HgCEMs did poorly, except Tekran and Thermo. Only the Tekran 3300 CEM was able to pass the Tekran 3300 CEM was able to pass allall USEPA Trial USEPA Trial performance performance measurements.measurements.
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Joint EERC, EPRI & ICCI ProjectJoint EERC, EPRI & ICCI ProjectDetermining the Accuracy of CMMs at Low Mercury ConcentrationsDetermining the Accuracy of CMMs at Low Mercury Concentrations
Figures adapted from Laudal et al., 2010 Figures adapted from Laudal et al., 2010
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NOTE: The coal result bias for the Thermo NOTE: The coal result bias for the Thermo
Freedom System was resolved on a second Freedom System was resolved on a second
test at EERCtest at EERC
Reliant Energy: Reliant Energy: HgCEM Accuracy HgCEM Accuracy -- low low
Hg Hg levels levels –– wet scrubber stack wet scrubber stack -- 20072007
�� Sorbent Traps (avg) = Sorbent Traps (avg) = 0.59 ug/m0.59 ug/m33
�� Tekran with M&C Tekran with M&C (avg) = 0.56 ug/m(avg) = 0.56 ug/m33
�� Slide courtesy of Eric Slide courtesy of Eric
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�� Slide courtesy of Eric Slide courtesy of Eric RolandRoland
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NOTE: Reliant Energy NOTE: Reliant Energy
is now NRGis now NRG
�� The coal flue gas The coal flue gas matrixmatrix is very challengingis very challenging
�� ConversionConversion of Hgof Hg2+2+to Hgto Hg00 quantitatively with longquantitatively with long--
term robustness is critical for successterm robustness is critical for success
�� Quantitative Quantitative transporttransport of Hg species from probe to of Hg species from probe to
Field Trials: Lessons Learned about Field Trials: Lessons Learned about
HgCEM System Design and Operation HgCEM System Design and Operation
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�� Quantitative Quantitative transporttransport of Hg species from probe to of Hg species from probe to
detector requires:detector requires:
•• Dilution with dry airDilution with dry air
•• High temperatures for HgHigh temperatures for Hg2+2+ -- no cold spotsno cold spots
•• Inert surface materials Inert surface materials
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�� 1 µg/m3 1 µg/m3 Hg = 112 Hg = 112 parts per trillion (v/v)parts per trillion (v/v)
�� Accurate measurements requires Accurate measurements requires
understanding and managing the many understanding and managing the many
potential mercury redox reactions potential mercury redox reactions with with
halogens, sulfur oxides and water halogens, sulfur oxides and water in the gas in the gas
MATRIX: Accurately Measuring pptv* MATRIX: Accurately Measuring pptv*
Levels of Mercury in Coal Flue GasLevels of Mercury in Coal Flue Gas
HgHg00
HgHgClCl22HClHCl
SOSO22
HH22OONONOXX
HBrHBr
SeSeFeFe
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phase and on surfaces phase and on surfaces
�� Tekran R&D spent 1998 to 2003 Tekran R&D spent 1998 to 2003
understanding flue gas mercury reactions understanding flue gas mercury reactions
in the lin the laborataboratoryory
�� Detectors can only measure HgDetectors can only measure Hg00
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HgHg00
BiBi--directional reactionsdirectional reactions
For analysis, HgFor analysis, Hg00 formation must be quantitative formation must be quantitative
with no back reactionwith no back reaction
CONVERSION: The Challenge of Mercury CONVERSION: The Challenge of Mercury
and Reactive Halogensand Reactive Halogens
�� HgHg00 + reactive halogen is our + reactive halogen is our
friend and foe:friend and foe:
•• Required for Hg analysis by HgCEMRequired for Hg analysis by HgCEMss
and direct thermal method for and direct thermal method for
sorbent traps (30B)sorbent traps (30B)
•• Helpful for Hg control and used for Helpful for Hg control and used for
HgHgClCl2 2 HgHg00 + + ClCl22
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For For control, HgXcontrol, HgX22 formation formation and capture needs to and capture needs to
be quantitative be quantitative with no back with no back reaction to minimize reaction to minimize
release of Hgrelease of Hg00
Simplified chemistry for illustration Simplified chemistry for illustration
purposes onlypurposes only
•• Helpful for Hg control and used for Helpful for Hg control and used for
HgCEM performance checksHgCEM performance checks
�� BiBi--directional reaction affected by directional reaction affected by
•• TemperatureTemperature
•• Catalytic surface reactionsCatalytic surface reactions
•• Gas and particle matrixGas and particle matrix
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HgHg00 ++ BrBr2 2 HgHgBrBr22
Tekran 3300Xi HgCEM Converter Flue Gas Tekran 3300Xi HgCEM Converter Flue Gas
Converter/Conditioner (patented)Converter/Conditioner (patented)
�� Proprietary thermal converter Proprietary thermal converter
material set at 700 degrees Cmaterial set at 700 degrees C
�� DI water injected into tail of DI water injected into tail of
thermal converter to “fix” Hgthermal converter to “fix” Hg00
from potential back reactions and from potential back reactions and
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from potential back reactions and from potential back reactions and
eliminate interferenceseliminate interferences
�� Gas is rapidly chilled, water Gas is rapidly chilled, water
condenses and removes reactive condenses and removes reactive
compoundscompounds
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TRANSPORT: HgCEM design to minimize TRANSPORT: HgCEM design to minimize
transport reactions and lossestransport reactions and losses
�� 30:1 dilution with dry zero air (can be higher)30:1 dilution with dry zero air (can be higher)
�� Filter element and related surfaces made with inert coatings and frequent Filter element and related surfaces made with inert coatings and frequent
system blowbacks (hourly)system blowbacks (hourly)
�� For umbilical lines, must use fluoropolymer tubing (PFA, FEP), heat to 180˚ For umbilical lines, must use fluoropolymer tubing (PFA, FEP), heat to 180˚
C, no cold spotsC, no cold spots
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C, no cold spotsC, no cold spots
�� Thermal converter catalyst material is robust and surface chemistry has Thermal converter catalyst material is robust and surface chemistry has
been characterized and is knownbeen characterized and is known
�� Inject fresh DI water after the thermal converter and rapidly drop the Inject fresh DI water after the thermal converter and rapidly drop the
temperature, to chemically “fix” Hgtemperature, to chemically “fix” Hg00 and prevent Hg(II) reand prevent Hg(II) re--formation by formation by
back reactions with reactive halogens or other compounds (Tekran only)back reactions with reactive halogens or other compounds (Tekran only)
•• In effect, a mini wetIn effect, a mini wet--scrubber with chilled coalescing filterscrubber with chilled coalescing filter
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MERCURY CONTROL RESEARCH, MERCURY CONTROL RESEARCH,
EQUIPMENT AND EXAMPLE RESULTS EQUIPMENT AND EXAMPLE RESULTS
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Tekran 3300RS (Research Systems)Tekran 3300RS (Research Systems)
3300RS3300RS--Dual ProbeDual Probe 3300RS Upstream Injection3300RS Upstream Injection
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Schematic Schematic of of Johnson Matthey Johnson Matthey
Catalyst Testing Equipment Catalyst Testing Equipment
FTIR
Simulated Power
Plant Exhaust gas
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Heated Reactor
with catalyst
Tekran
3300RS Dual
Port system
FTIR
analysis
SO3
analysis
Reactor Outlet Slide courtesy of Michael Nash Slide courtesy of Michael Nash
at Johnson Mattheyat Johnson Matthey
Johnson Matthey 3300RS Johnson Matthey 3300RS Dual Port Dual Port
System and Test Rig ConfigurationSystem and Test Rig Configuration
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Slide courtesy of Michael Nash Slide courtesy of Michael Nash
at Johnson Mattheyat Johnson Matthey
Example Example data data from Johnson Mattheyfrom Johnson MattheyConversion of HgConversion of Hg00 to Hgto Hg2+2+ across a catalystacross a catalyst
Online measurement of Online measurement of
flue gas components flue gas components
during simulated power during simulated power
plant conditions. plant conditions.
Condition 1: a low Condition 1: a low
halogen bituminous halogen bituminous
condition condition
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condition condition
Condition 2: a high Condition 2: a high
halogen bituminous halogen bituminous
condition condition
Slide courtesy of Michael Nash Slide courtesy of Michael Nash
at Johnson Mattheyat Johnson Matthey
Mercury Research Configuration at Mercury Research Configuration at
Shanghai Jiaotong UniversityShanghai Jiaotong University
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Reactor and sorbent performance Reactor and sorbent performance
evaluation with controlled Hg source evaluation with controlled Hg source
and Tekran 3300RS Unitand Tekran 3300RS UnitSlide courtesy of Professor Yan Slide courtesy of Professor Yan
NaiQiang at Shanghai Jiaotong NaiQiang at Shanghai Jiaotong
UniversityUniversity
�� Conversion of HgConversion of Hg00
to Hgto Hg2+2+
�� Good mass balance Good mass balance
Example Mercury Research Results fromExample Mercury Research Results from
Shanghai Jiaotong UniversityShanghai Jiaotong University
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�� Good mass balance Good mass balance
�� Good recovery to Good recovery to
zero Hg zero Hg –– no no
memory effect memory effect
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Slide courtesy of Professor Yan NaiQiang at Shanghai Slide courtesy of Professor Yan NaiQiang at Shanghai
Jiaotong UniversityJiaotong University
U. of NingboU. of Ningbo--Nottingham Hg Control Nottingham Hg Control
Technology Configuration with 3300Technology Configuration with 3300--RSRS
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Slide courtesy of Dr. Tao Slide courtesy of Dr. Tao
Wu’s Research Lab at the Wu’s Research Lab at the
U. of NingboU. of Ningbo--NottinghamNottingham
� Mainly used for parametric
studies of both fresh and
deactivated catalyst
� The reactor is a fully
automated and continuous
system capable of injecting
a wide variety of gaseous
Cormetech MicroCormetech Micro--Reactor Schematic Reactor Schematic
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a wide variety of gaseous
and aqueous species
� Capable of measuring
DeNOx, SO2 oxidation,
and Hg0 oxidation over a
single layer
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Slide courtesy of CormetechSlide courtesy of Cormetech
�� This Tekran 3300RS was This Tekran 3300RS was
designed to provide known designed to provide known
upstream input of upstream input of HgHg00 and and
HgHg2+2+ using a custom using a custom
injection moduleinjection module
Cormetech Reactor & Tekran 3300RS UnitCormetech Reactor & Tekran 3300RS Unit
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injection moduleinjection module
�� Installed in a vented Installed in a vented
enclosureenclosure
2222Slide courtesy of CormetechSlide courtesy of Cormetech
�� Reactor is fully automated, Reactor is fully automated,
using preusing pre--defined testing defined testing
sequence and stability sequence and stability
criteriacriteria
�� Automated allows many Automated allows many
factors to be testedfactors to be tested
Cormetech Example of an HgCormetech Example of an Hg00 Trend Trend
for a Continuous Hg Testfor a Continuous Hg Test
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factors to be testedfactors to be tested
�� Factors affecting HgFactors affecting Hg00
oxidation are temperature, oxidation are temperature,
AV, and HgAV, and Hg00, NH, NH33, SO, SO22, CO, , CO,
HCl, and HBr HCl, and HBr
concentrationsconcentrations
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Slide courtesy of CormetechSlide courtesy of Cormetech
�� Full Speed Ahead for USA Hg Emission Regulations after long Full Speed Ahead for USA Hg Emission Regulations after long
run of HgCEM equipment performance trialsrun of HgCEM equipment performance trials
�� For research and monitoring, the HgCEM design must deal For research and monitoring, the HgCEM design must deal
with the flue gas with the flue gas matrixmatrix, Hg, Hg2+2+to Hgto Hg00 conversionconversion and and transporttransport
challenges in order to get accurate resultschallenges in order to get accurate results
ConclusionsConclusions
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challenges in order to get accurate resultschallenges in order to get accurate results
�� In the mercury control research laboratory, there are now In the mercury control research laboratory, there are now
custom HgCEM units to help develop and commercialize custom HgCEM units to help develop and commercialize
control technologycontrol technology
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