Methods for Continuous

Emission Gas Monitoring

 Factors to consider when
choosing a CEM System
• Compliance with Legislation

• Suitable Analytical Method

• Appropriate Analytical Techniques

• Correct System Design

• Reliability & Availability

• Overall operating Cost

 Compliance with Legislation

• For any given process, the Legislation

imposes limits on how much can be emitted
to the atmosphere for particular species

• These limits can be expressed as:

– Maximum gas concentration

• ppm
• mg/m3

– Maximum mass emission

 Gas Concentration

• When the limits imposed specify gas

concentration, it must often be expressed at
the following conditions:

– Dry basis

– Temperature: 0 deg C (273 K)

– Pressure: 1 atm. (101.3 KPa)

– Corrected for the O2 level specified for the given process

 To comply with most
Legislation,ideally,all gases
should be measured on a dry
basis, i.e after removal of water.
However, certain gases must be
measured in a hot wet state
because:
• They are soluble in water

• They would otherwise condense and lose

their gaseous state
 Factors to consider when
choosing a CEM System
• Compliance with Legislation

• Suitable Analytical Method

• Appropriate Analytical Technique

• Correct System Design

• Reliability & Availability

• Overall operating Cost

 Analytical Methods available

• In Situ

• Dilution Probe

• Extractive
In Situ - Optical Cross Stack

U.V or I.R

flue
gas
 In Situ - Optical Cross Stack

Advantages:

• Low installation cost

• No sample system required

 In Situ - Optical Cross Stack
Disadvantages:
• True traceable calibration not possible
• Wet gas basis only
• Difficult access for maintenance
• Significant interferences
• Limited sensitivity
• Temperature limitation
• Not suitable for applications with high dust
loading
• Requires separate O2 and moisture
measurements
• Does not normally measure NO2
 Dilution Probe

dilution
probe

flue pump &

calibration
gas

analysers

clean air
 Dilution Probe
Advantages:

• In-situ conditioning

• Low extraction rate

• Quenches most reactions

• No heated lines

• No corrosive gases transported

 Dilution Probe
Disadvantages:
• Wet gas basis only
• Requires purified air
• Requires separate O2 and moisture measurements
• Problems with ambient air analysers
• Slow response time
• Single dilution ratio
• Needs tracer gas at probe to verify dilution ratio
• Does not operate at high temperature
 Extractive Method

sample transport line

probe
sample
flue conditioning
gas
analysers

calibration
 Extractive Method
Advantages:
• Dry and wet analysis
• Ease and accuracy of calibration
• Ease of maintenance
• Integral O2 and moisture measurements
• Analysers run under controlled conditions:
high stability
• Optimal control of sample conditioning
• Much more accurate analysis
 Extractive Method

Disadvantages:

• Needs heated lines (when hot analysis

required)

• Needs sample conditioning

 Factors to consider when
choosing a CEM System
• Compliance with Legislation

• Suitable Analytical Method

• Appropriate Analytical Technique

• Correct System Design

• Reliability & Availability

• Overall operating Cost

 The Choice of Analytical
Technique depends on the Gas
Species. The main Gases are:
• CO : Carbon Monoxide
• CO2: Carbon Dioxide
• NO : Nitric Oxide
• NO2: Nitrogen Dioxide
• NOx: Nitrogen Oxides ( NO+NO2)
• SO2: Sulfur Dioxide
• HCs: Hydrocarbons (Volatile Organic
Compounds: VOCs)
• O2 : Oxygen
• Others – HCl, HF
 Carbon Oxides:

• CO and CO2 normally measured by Infra Red

• With Infra Red, water vapour interference

• Therefore, dry analysis (after removal of

water)
 Sulphur Dioxide:
• SO2: Slightly soluble.

• Prolonged contact with water generates corroding

acid.

• Can be analysed in dry condition if transported in hot,

wet condition and water removed quickly by chilling
sample.

• IR: dry analysis

• UV: wet or dry analysis, only if no HCs in flue gas

Dispersive and Non-Dispersive
Optical Techniques

Light is re-emitted or scattered in all directions

 Beer’s Law
Absorption of light follows Beer’s Law which states that the
degree of absorption of light varies exponentially with the
thickness of the layer of absorbing medium, it’s molar
concentration and it’s absorption constant.
Mathematically this is:

I = Io exp(-axc)
I = Intensity of light after absorption
Io = Intensity of light before absorption
a = Absorption constant (different for each gas)
x = Absorption path length
c = Concentration
If path length is chosen to suit a particular concentration range,
then the response of an analyser to varying concentrations will
be of this nature:
 Single Beam NDIR

chopper
blade
motor
optical filter
sample cell

I.R.
source

detector

sample sample
in out
 Gas Filter Correlation NDIR
Gas filter wheel

motor
detector
sample cell

I.R.
source

optical
filter

sample sample
in out
 Dual Beam NDIR

chopper
reference
synchronous blade
cell
motor

flow
I.R. detector
source

sample
cell

sample sample
in out
 Other optical techniques

• Fourier Transform Infrared – very useful for

investigative work, but requires very skilled
operatives and all components have to be
referenced. It is also expensive.
• FT-IR is good for N2O and can analyse
multiple components simultaneously

• Laser based systems – precise wavelength,

usually use IR or visible frequencies, in-situ
location.
 Nitrogen Oxides:

• 3 techniques: Infra Red, Ultra Violet and

Chemiluminescence.

• Infra Red requires dry analysis.

• With Ultra Violet, Hydrocarbons interference.

• Chemiluminescence, very sensitive

technique, not affected by water or
Hydrocarbons.
 Nitrogen Oxides

• NO2 is very soluble in water. Must be

maintained at temperature above water dew
point.

• NO: dry analysis if IR ;dry or wet analysis if

UV (only when no HCs in flue gas) or
Chemiluminescence.

• NO/NO2/NOx: wet analysis only, UV (when no

HCs in flue gas) or Chemiluminescnce
 Chemiluminescence
clean
dry
air reaction chamber
O3 generator

photomultiplier
tube (PMT)

--------signal

to vent

pump

NO + O3 ---> NO2* + O2
sample
NO2 / NO converter NO2* ---> NO2 + hv
 Hydrocarbons:

• Must be analysed in a hot, wet condition as

would otherwise condense.

• Normally analysed by Flame Ionisation

Detection (FID)
Flame Ionisation Detector (FID)
gas outlet

anode

ionisation air
current

cathode

sample H2 + He
 Oxygen:

• Two techniques: Paramagnetic and Zirconia

Paramagnetic:
• Dry analysis only
• Susceptible to corrosion and damage by
water
• NO2 interference

Zirconia:
• Rugged and reliable
• Wet or dry basis
 Oxygen
• Zirconia probe – electrochemical sensor,
using zirconia at 800 centigrade

Outer electrode

Inner electrode

Reference air

Sample stream

At 800 degrees the Zirconia becomes a solid electrolyte and O2 will

migrate from the high to low concentration to maintain an equilibrium.
Usually from the reference to the sample.
 Factors to consider when
choosing a CEM System
• Compliance with Legislation

• Suitable Analytical Method

• Appropriate Analytical Technique

• Correct System Design

• Reliability & Availability

• Overall operating Cost

 Correct System Design :
Aspects to consider.
• Sample extraction & transportation

• Sample Conditioning

• Analysis

• Calibration

• Data collection

• Housing
 Sample Extraction : Typical
Probe.

Cal gas and

air for
blow back

sinter To
heated
line
Heated compartment

flue
gas
ON-STACK PROBES
 Sample Extraction : Factors to
consider.

• Stack temperature

• Dust loading

• Corrosiveness
 Sample Transport : Typical
heated Line.

Teflon/PFA core
Steel braid

heating element

electrical insulation

thermal insulation

scuff resistant jacket

 Sample Conditioning :

• Wet analysis (keeping sample in hot and wet

condition)

• Dry analysis (removing water from sample) :

• Mixed analysis (splitting sample into wet and

dry streams)
 Sample Conditioning for Wet
Analysis : Moisture
Measurement.
• To comply with the legislation, the moisture
must be measured so that the correction for
water can be made.

• Main moisture measurement techniques:

• Chilled mirror
• RH sensor
• Dual O2 measurement
 Moisture Measurement
Chilled Mirror & RH sensors

• Chilled mirror systems- Accurate but very

difficult to use and very expensive.

• RH sensors – cost effective but not robust in

hot and dirty atmospheres
 Moisture Measurement : Dual O2
Measurement

Zirconia Zirconia

O2 wet O2 dry

( O2 Wet )
microprocessor % (H2O) = 100 { 1-
( O2 Dry )
}
%moisture
 Moisture Measurement :
Dual O2 Measurement
Advantages:
• Continuous measurement
• No extra stack insertion (if using extractive)
• Not affected by stack conditions
• Not temperature dependent
• Rugged
Disadvantages:
• Restricted accuracy at low O2 level
 Sample Conditioning for Dry
Analysis : Removal of Water.
• Two factors can affect the performance of an analyser
after removal of water: residual acids and residual
hydrocarbons.

• When choosing the water removal technique,it is

therefore vital to consider the levels of acids and
hydrocarbons generated by the process.

• Main methods:
– Front end permeation dryer
– Chiller
 Removal of Water : Front End
Permeation Dryer

wet purge
gas

sample wet -- -- -- -- -- -- -- -- -- -- --
- ------------------------------------- sample dry
desiccant membrane

dry purge
gas
 Removal of Water : Front End
Permeation Dryer
Advantages:
• Low cost
• No heated line needed
• Removes water while in gaseous phase: no
problems with solubility of SO2, NO2 etc..
 Removal of Water : Front End
Permeation Dryer
Disadvantages:
• Desiccant membrane easily clogged up by
hydrocarbons and other sticky condensates
• Does not remove acids and some
hydrocarbons.
• Removes some HCs and NH3
• Results affected by ambient temperature
variations
• Unpredictable stabilisation time
• No efficiency checks possible
 Removal of Water : Chiller
1= Sample probe
2= Heated line
3= Dual path chiller
4= Sample pump
1 5= Condensate sensor
6= Filter coalescer

4 to analysers
5 6
flue .. .. .. .. .. .. .. .. .. .. .. .. .. .
gas : :
: :
: 3 :
:. .. .. .. .. .. .. .. .. .. .. .. .. ..:
 Removal of Water : Chiller
Advantages:
• Verification of efficiency possible through
temperature measurement
• Very robust, reliable, well proven method
• Quick water removal minimises solubility
problems
• No dirty condensate problems
• Maximum removal of acids and hydrocarbons
Disadvantages:
• Higher cost
• Needs heated line
 Extractive Sample Conditioning
for Mixed Analysis (wet and dry)

probe
heated
HCs
line

NOx
heated
module
with flow O2
control (wet) moisture
O2
(dry)
chiller with SO2
flow control
system CO
control

CO2
 Calibration.

• Normally made using traceable gases from

bottles certified for the right concentration
(within the range chosen)

• Calibration gases can be inserted, either

directly at the analysers, or, via the probe,
through the line and the sample conditioning
system so as to verify the system integrity.

• New guidance requires more calibration

points, use of dilutors and dividers
Having now carefully considered
the following Aspects :
• Compliance with Legislation
• Suitable Analytical Method
• Appropriate Analytical Technique
• Correct System Design
Check your supplier and the
equipment for:

Reliability & Availability

Value for money
Service and support