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Art & Science of Continuous

Emissions Monitoring Systems

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ISA – LONG ISLAND
NEW YORK SUB SECTION

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ENVIRONMENTALIST
DATES BACK TO 13TH CENTURY

KING EDWARD I OF ENGLAND

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Overview
• CEMS Methodologies
– Extractive, Dilution, In-Situ etc
• Common measurements and analytical
approaches
• Common Problems in the different
methodologies

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CEMS Technologies
 Continuous emission monitoring
or automated measuring systems
can be categorised into two
types:
 Type 1: Extractive systems
 Type 2: In situ systems

 Extractive systems withdraw flue


gas continuously from stack and Extractive monitoring system
transport it to the analyser.

 In situ systems carry out most of


their operations in the stack.
 Point in situ carry out analysis at In situ monitoring
system.
a single point in the stack.
 Path monitors carry out analysis
usually over the entire stack.

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Extractive Systems
Gas is extracted from the stack and
transported to a CEMS shelter and
analyzed.

• Components of an extractive system:


* Probe
* Particulate filter (s)
* Moisture conditioning system
* Pump
* Controller
* Analyzers
* DAHS
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Extractive System Components
• Sample probe
• Probe blowback
• Sample line
• Moisture conditioning System
• Pumps
• Valves and Fittings
• Pressure and Vacuum Meters
• Filters
• Cabinets
• Shelter
• Shelter heating/air conditioning system
• Electrical Support/UPS
• System Controller
• Calibration Gases
• Gas Distribution System

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Extractive Systems
Extract sample gas from the duct or stack to analyzers in a
CEM shelter, cabinet, or close-coupled to the stack.

Source Level
• Cool-dry
• Hot-wet
Dilution
• In-stack
• Out-of-stack

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Extractive Systems
Advantages and Disadvantages
Advantages
• Versatility — Easily modified and expanded
• Ease of maintenance
• Accept calibration gas standards
• Flexibility in sampling locations/configurations

Disadvantages
• May alter sample
• Response time may be slow
• Capital costs may be high
• Maintenance frequency and costs may be high

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Cool-Dry Extractive Systems
Sample gas is extracted and conditioned to remove moisture
prior to analysis. Options:

• Conditioning at the CEM shelter


Heated sample line is required to keep the wet sample above its
dew point until it reaches the water removal system
• Conditioning at the stack
Water is removed at the stack - no heated line - commonly used
by source testers for short-term sampling

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Cool-Dry Extractive Systems
Advantages
• Flexibility in the choice of analyzers and types of gases measured
• Moisture interference in analyzers minimized
• Maintenance is straightforward

Disadvantages
• May alter sample
• Numerous components - higher maintenance
• May be high cost option
• Require H20 monitoring if reporting in lbs/hr (wet basis)

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Hot-Wet Extractive Systems
No moisture removal - Moisture remains in the
system throughout the sampling and measurement
process.

Sampling line, pump, and analytical chamber are


heated to keep wet sample gas above its dew point.
Sample is analyzed hot and wet.

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Hot-Wet Extractive Systems
Advantages
• Water soluble gases can be sampled without losses in chillers
(good for acid gases, VOCs)
• Gas is measure on a wet basis for reporting in lbs/hr
• Fewer parts than cool-dry systems

Disadvantages
• Components at elevated temperatures may have shorter lifetimes
• Loss of heating can cause, corrosion, pluggage, and system damage
• water must not interfere in the analytical measurement

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In-Stack Dilution Systems
Flue gas sample is diluted with clean/dry air using a
"dilution probe" inside the stack

• Sample gas is diluted (typically at ratios of 15 to 300 to 1) with dry


gas at dew points typically at
- 40° C
• Dilution ratio controlled by using a critical orifice in the probe -
critical flow maintained by achieving a set pressure drop across
orifice
• Flow through orifice is dependent on Ts, Ps, Ms, and dilution air
pressure and temperature.
• A "wet" gas measurement is made
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In-Stack Dilution Systems
Advantages
• Fast response time
• Fewer components than source-level systems
• May be applied for water soluble gases
• Capital and maintenance costs can be lower
than source-level systems
Disadvantages
• Limited by analyzer range (inability to measure diluted
concentrations, e.g. CO, HCl, NH3)
• Dilution ratio dependent on Ts, Ps and Ms
• Difficult to calibrate in cycling units
• Droplets can plug critical orifice
• Probe must be extracted from stack for maintenance
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Out-of-Stack Dilution Systems
Flue gas sample is diluted with clean/dry air using dilution "box"
close-coupled or otherwise outside of the stack

• Dilution ratio controlled by using a critical orifice in the box - critical


flow maintained by achieving a set pressure drop across orifice
• Sample gas is diluted (typically at ratios of 15 to 300 to 1) with dry gas
at dew points typically at
• - 40° C
Flow through orifice is dependent on Ps, Ms, and dilution air pressure
• and temperature.
A "wet" gas measurement is made

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Out-of-Stack Dilution Systems
Advantages
• Fewer components than source-level systems
• May be applied for water soluble gases
• Not overly dependent on stack temperature (can be applied to cycling units)
• Avoid problems with droplets/orifice plugging
• Capital and maintenance costs can be lower
than source-level systems
• Systems can designed to split sample flow for drying
• Maintenance can be performed without removing probe
Disadvantages
• Limited by analyzer range (inability to measure diluted concentrations, e.g. CO,
HCl, NH3)
• Dilution ratio dependent on Ps and Ms
• Slower response time than in-stack probes

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In-Situ Systems
Measure gases, flow, or particulate matter in the duct or stack
without gas extraction

• Path Systems
Transmit light or sound across the duct or stack to make the
measurement.

• Point Systems
Make measurements at a point or short sensing volume (cm to
m) in the stack or duct.

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In-Situ Monitoring Techniques
• Opacity
Single-pass or double-pass optical measurements

• Flue Gas Flow


Path or point (ultrasonic or audible sound)
Path (optical time-of-flight, scintillation)
Point (differential flow, thermal sensors, ultrasonic)

• Pollutant and Diluent Gases


Path (single-pass or double-pass electro-optical)
Point (short path light scattering)

• Particulate Matter
Path (light extinction (transmissometers), received light modulation)
Point (light scattering (short path))
Point (triboelectric charge transfer, impaction electrodynamic induction)

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In-Situ Systems Advantages and
Disadvantages
• Advantages
– Lower Cost (Fewer components, no shelters)
– Do not alter sample
– Fast response times
– Less maintenance than for extractive systems
– Wet-basis measurement

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In-Situ Systems
• Disadvantages
– Little flexibility, not easily modified
– Monitor problems may be difficult to resolve
onsite
– May not have ability to be audited with Protocol
gases
– Calibration methods not always done with
independent standards
– May be subject to severe environmental
conditions (heat/cold, lightning strikes)

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Analytical Methods
• Common Species
– Sulfur Dioxide SO2
– NOx CO
– Oxygen
– Ammonia
– Mercury
– H2S
– CO2
– VOC’s

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Sulfur Dioxide
• One of the most common measurements in all
combustion processes
Method Technique Technology Advantages Disadvantages
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Simple, proven, Interference
Infrared (NDIR) Cold dry ex-situ Filter photometer Cost-effective (water and CO2)
In-situ Multi-component Non-linearities
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Simple, Proven, Difficult to do very
Ultraviolet Cold dry ex-situ Filter Photometer Cost effective low
In-situ Multi-component concentrations
UV Fluorescence Cold Dry Ex-situ Excitation (214nm) Highly Specific Hydrocarbon
Dilution Extractive and Fluorescence High Sensitivity interference,
(300 nm) Quenching
Dispersive In-Situ Beer Lambert Multicomponent Calibration,
Ultraviolet Dispersive Temperature
effects

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Nitrogen Oxides
• Perhaps most common priority pollutant
Method Technique Technology Advantages Disadvantages
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Simple, proven, Interference (water
Infrared (NDIR) Cold dry ex-situ Filter photometer Cost-effective and CO2)
In-situ Multi-component Non-linearities
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Simple, Proven, Difficult to do very
Ultraviolet Cold dry ex-situ Filter Photometer Cost effective low concentrations
In-situ Multi-component Interferences
Chemiluminescence Cold Dry Ex-situ React NO with O3 Highly Specific Hydrocarbon
Dilution Extractive and measure High Sensitivity interference,
emissions Quenching
Dispersive In-Situ Beer Lambert Multicomponent Calibration,
Ultraviolet Dispersive Temperature
effects and
Interference

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Carbon Monoxide
• Little interest as a pollutant – more about
combustion control
Method Technique Technology Advantages Disadvantages
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Simple, proven, Interference
Infrared (NDIR) Cold dry ex-situ Filter photometer Cost-effective (water and CO2)
In-situ (GFC) Multi-component Non-linearities
Tunable Diode In-Situ Wavelength Very Specific and Expensive, may
Laser Modulation Sensitive require air purge
Spectroscopy on optics

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Oxygen
• Not a pollutant – measure for combustion
control or as diluent
Method Technique Technology Advantages Disadvantages
Paramagnetic Hot Wet ex-situ Measures unique Simple, proven, Corrosion of
Cold dry ex-situ magnetic effect of Cost-effective “dumbell” type,
oxygen sensitivity
Zirconium Oxide Hot Wet ex-situ Transport of Simple, Proven, Bias by
Cold dry ex-situ oxygen ions Cost effective combustibles,
In-situ (Nernst Eqn) corrosion
Tunable Diode Laser In-Situ Wavelength Highly Specific Expensive, may
Cold Dry ex-situ Modulation Good Sensitivity require air purge
Hot Wet ex-situe Spectroscopy Can do on optics,
Temperature

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Ammonia
• Increasingly common with SCR / SNCR and
NOx reduction
Method Technique Technology Advantages Disadvantages
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Multi-compent Interference (water and
Infrared (NDIR) In-situ Filter photometer CO2)Non-linearities
Sensitivity
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Multi-component Interference.
Ultraviolet In-situ Filter Photometer Sensitivity
Chemiluminescence Cold Dry Ex-situ Special Converter in Fits well with Differential – can have
Dilution Extractive? probe Standard NOX sensitivity issues
systems
Dispersive Ultraviolet In-Situ Beer Lambert Multicomponent Calibration, Temperature
Dispersive effects and Interference
Tunable Diode Laser In-Situ Wavelength Highly Specific Expensive, may require
Modulation Good Sensitivity air purge on optics,
Spectroscopy

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Mercury
• Primarily for coal fired generating stations
Method Technique Technology Advantages Disadvantages
Atomic Absorption Hot Wet ex-situ Beer Lambert Law Can be Less Sensitivity than
Cold Dry ex-situ Resonance Mercury continuous Fluorescence
emission
/absorption
Atomic Fluorescence Hot Wet ex-situ Similar to SO2 High Sensitivity Batch Sampling
fluorescence and specificity
analyzer

Most Mercury CEMS use common parts including an inertial filter probe for particulate
removal, often an absorbing media to absorb mercury and perform batch analysis, and a
converter to converter oxidized Mercury to elemental mercury. Many issues are still
percieved with this difficult measurement.

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Hydrogen Sulfide
• H2S, Total Sulfur (TS), Total Reduced Sulfur (TRS)
Method Technique Technology Advantages Disadvantages
Lead Acetate Tape Cold Dry Ex-Situ Stain PbO to PbS Sensitive, specific Accuracy, tape reliability
Dilution ?
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Multi-component Interference.
Ultraviolet Cold Dry ex-Situ Filter Photometer Sensitivity
Chromatography Cold Dry Ex-situ Gas Specific, Expensive, Maintenance
Dilution Extractive? Chromatography Speciates,
and sulfur specific Multicomponent
detector (FPD)
UV Flourescence Extractive Fluorescence with Sensitive Non-specific Total Sulfur
thermal conversion or Total Reduced Sulfur
to SO2
Tunable Diode Laser Cold Dry Extractive Wavelength Highly Specific Expensive, interferences
Hot Wet Extractive Modulation
Spectroscopy

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Carbon Dioxide
• Was measured as an estimator of fuel usage, but
GHG emissions now “important”
Method Technique Technology Advantages Disadvantages
Non-Dispersive Hot Wet ex-situ Beer Lambert Law Simple, proven, Interference
Infrared (NDIR) Cold dry ex-situ Filter photometer Cost-effective (water )
In-situ (GFC) Multi-component
Tunable Diode In-Situ Wavelength Very Specific and Expensive, may
Laser Modulation Sensitive require air purge
Spectroscopy on optics

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Volatile Organic Carbon
• Unburned hydrocarbons in stacks, emissions from
vapor recovery units, etc
Method Technique Technology Advantages Disadvantages
Flame Ioization Hot Wet ex-situ Hydrogen flame Proven, good Maintenance, no
Detector (FID) and measure sensitivity specificity
hydrocarbon ions
Gas Hot Wet Ex-Situ GC separation and Very Specific and Expensive, batch
Chromatography FID detection Sensitive measurement
Mass Hot Wet ex-situ Mass selective Fast and Maintenance and
Spectrometery detector looking at continuous calibration
particular peaks

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Common Issues
• Extractive Systems • In-Situ Systems
– SO3 and Acid – Calibration
Dewpoints – Opacity
– Ammonia Salt – Obfuscation
formation
– Particulate
– Water and Cold Spots
– Dilution Air purity

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SO3 and Acid Dewpoints
• Sulfur Trioxide formed by:
– SO2 + 1/2O2 SO3
– SO2 + NO2  SO3 + NO
– Note reactions catalyzed by metals (vanadium)
– Coal/refinery residues often contain such metals
• Factors which increase SO3
– High temperature combustion
– High sulfur content
– Excess O2
– Catalyst fines

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SO2 systems
• Sources of Bias to be considered
– Catalyst fines and other physical contamination at the probe
• Sulfur dioxide may adsorb on particulate material
• Blowback systems are strongly recommended on sample probe systems
• FCCU – blowback is a must-have
• SRU stack – helps prevent catalyst fines but these may not make it past wet
scrubbers
• Wet scrubbing systems introduce new issues for emissions monitoring – scrubber
carryover and high water content
• Wet stacks (wet scrubber with no stack gas incineration) as may be seen in sulfuric
acid plants present other problems – blowback removes liquid contamination.
– Particulate filters / Coalescing Filters have lots of surface area
• These are potential sources of bias and should be investigated
– Sulfur Dioxide is water soluble
• Dryer performance should be tested as well as a potential source of bias
– Sample Lines – Electropolish with Sulfinert provides inert surface

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Ammonia Salts
• Ammonia reacts with acid gases to form salts
(ammonium sulfate, ammonium nitrate)
• Salts plug off filters, lines, and act as powerful
adsorption sites
• Three solutions
– Scrub them with a dry scrubber
– Phosphoric acid injection
– Temperature – salts dissociate when hot

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Particulate
• Particulate – whether scales, coal fines,
catalyst fines etc can cause problems
• Plugging an obvious one
• Catalysis another – converts SO2 to SO3
• Adsorption desorption sites and slow
response speeds

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Adsorption Effects
• As we move to lower and lower
concentrations adsorption on surfaces
becomes more important
• Sample lines, filters, etc need to be carefully
considered
• Heat is your friend

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Water and Cold Spots
• Cold dry systems – water dropping out is a
major problem.
• One wet spot in the sample transport system
can greatly affect response speed and
calibration reproducibly
• Impinger / dryers designed to be wet but not
give much adsorption

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In Situ Systems
• In-situ systems tend to have different
problems than extractive systems
• Problems are less observable as well - often
only come up at RATA time

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Point Monitors
• Blinding
– Precipitate on the filter seals the probe tip fromthe
flue gas.
• Faulty Audit
– Improper flow rate of calibration Gas Injection gases
results in biased following calibration concentrations
in probe cavity. procedures.
• Temperature
– If temperature sensors are not Distortions working
properly, errors can result in emission values.

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Path Monitors
• Internal Calibration Cell Defects
– Errors are introduced when the internal
calibration cell leaks or gases decompose
• Gas Cell Temperature problems
– Bias introduced if gas cell not at same
temperature as stack
• Cal Gas Availability
– Short gas cells require high concentration gas,
which may not be available as protocol 1 gas

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Transmissometers
• Improper system design
– Some systems just never correlate well with visual
results
• Dirty Windows
– Build up on windows produces bias
• Interference
– Water droplets, NO2, acid droplets distort
measurements

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Summary
• A brief over of the complicated world of
emissions monitoring
• Many approaches each with merits and
disadvantages
• As with all analyzers, sample systems are
tremendously important

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Questions?
Cemtrex, Inc.
19 Engineers Lane,
Farmingdale, NY 11735
+1 631-756-9116
sales@cemtrex.com
mip.cemtrex.com
Ravi Narayan at rnarayan@cemtrex.com
Ronald Monte at rmonte@cemtrex.com
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