Document No:ES002
Date: August 01
Calibration of Gas Analysers
There are four separate aspects of calibration, as
follows:-
1. Foreword
2. Analyser Gain Setting/Zero Setting
3. System Verification
4. Linearity of Measuring Range
5. Traceability of Calibration Gas
6. NOx Generator
7. Soluble Gases
Foreword
Gas analysers are not absolute in measurement, they
only give a physical reading and need to be
compared with a gas of known concentration in order
to provide a reading of any calibrated amount.
Zeroing
The zero adjustment is normally done first using a
gas (typically Nitrogen) which is known to have no
gas being measured in it. You must set zero first
because this will affect reading throughout all
measuring levels and shown as an offset.
Analyser Gain Setting
Each analyser has a detector which responds to the
gas of interest. In order for the analyser reading to
be calibrated, a calibration gas of known
concentration is introduced directly to the analyser
and the reading adjusted by the analyser gain
controls so that it reads the correct value of the gas
cylinders.
System Verification
Normally, a gas analyser is sent a sample via a
sample line, filtration, cooler, pump etc.
In order to ensure that the sampling train integrity is
correct, it is very good practice to connect the
calibration gas to the sample point (ensuring no
leaks) and have it passed right through to the
analyser or analysers.
Any difference between the direct analyser calibration
and through the sample point will indicate a problem.
The problem could be leaks, absorption, dilution,
solubility etc. in the sample system and with this
produce an error in the reading of the analyser.
Normally, the analyser zero/gain settings against
calibration gas is adequate for routine calibration of
analysers.
The system verification should also be carried out
prior to any test program.
Linearity of Measuring Range
Calibrating analysers at one point is not enough. For
accurate readings it is important to audit the whole
range of the analyser using several separate points.
Checking this linearity is usually recommended on a
six monthly basis and it is not normally necessary on
a more regular basis.
You can check this by using several separate
calibration gases of different concentrations.
Normally 10 points is required.
A gas divider is a more convenient and accurate way
of splitting one calibration gas into 10 equal steps
which can then check the whole range of the
analyser.
Traceability
Obviously the calibration gas must be of the highest
accuracy and all gas suppliers quote their accuracies.
Source Testing Association
Unit 4, Theobald Business Centre, Knowl Piece,
Hitchin, Herts, SG4 0TY
Email Admin@S-T-A.org
NPL offer gases traceable to National Standards and
the USA NIST and UKAS.
You may choose to trust the certification of your gas
supplier, you may choose to have some NPL gases
to cross check from time to time the supplies from
your gas supplier or you may obtain your gases from
NPL for all your work. UKAS approved gases
normally means that they have been cross
referenced to NPL gases at the calibration lab of the
gas supplier.
Cross reference means that a linearized analyser in
the lab is calibrated using an NPL calibration gas and
then the gas suppliers own gas is introduced to the
same analyser and the reading is written on the
suppliers certificate. This is the traceability.
NOx Generator
Most NOx analysers only measure NO (Nitric Oxide)
the NO2 part of NOx is converted to NO using a NO2
to NO converter. NO2 + NO = NOx. From time to
time it is important to check if the NO2 converter is
working.
The amount of NO2 as a percentage of NOx varies
with application. From normal combustion sources
NO2 is about 5% of the NOx but from gas turbines the
NO2 is nearer 50% due to the amount of air in the
combustion process. Also, as NO comes from
combustion and moves into the atmosphere it
generally becomes NO2 in a very short period of time
in the oxygen laden atmosphere.
Therefore, the requirement for converter checking is
most critical with gas turbine combustion emissions.
In order to check a NO2 converter you must use NO2
calibration gas passing through the NO2 converter to
verify that it is reading at least 95% of its value on the
analyser compared to that of NO calibration gas.
To avoid errors in two gases it is more accurate to
use a noxgen instrument.
This device uses ozone, internally produced, to
change (oxidise) the NO calibration gas to NO2 in a
one for one reaction. The device finally allows you to
send NO calibration gas directly to the analyser for
gain setting and this is done in the NO mode i.e.
bypassing the NO2 converter.
The noxgen allows you to then start ozone generation
in increments so that the NO is converted to NO2.
The reading on the analyser in NO mode starts to
reduce as the NO is changed to NO2.
Once you have reached a certain level you change
the analyser mode to NOx which passes the
calibration gas through the NO2 converter and you
must see at least a 95% increase from the reduced
reading. The NO2 converter having changed the NO2
back to NO.
Soluble Gases
The most problematical of calibrations is with soluble
gases - those which dissolve in water.
Those given which are soluble in water and normally
associated with stack gas measurement are as
follows:-
A SO2
B NO2
C HCL
D NH3
SO2 is normally found in relatively high
concentrations in coal/oil combustion and the errors
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Document No:TGN001
with solubility are not significant until you are
measuring on the 100 ppm range.
At this level great care must be taken to ensure that
all sampling components are heated to ensure that
NO condensation occurs and that the water removal
device removes all free water on a continuous basis.
Calibrating the analyser directly on calibration gas will
set the measuring gain of the analyser but
subsequent connections of the same calibration gas
to the sampling point may indicate a lower reading if
there is any water in the sampling system which will
have dissolved some of the calibration gas.
The fact that the calibration gas comes from a
cylinder and is very dry, makes this situation worse as
it will take many hours for this gas to equilibrate with
the water vapour present in the sampling system
following stack gas sampling.
At the 100 ppm range of measurement all of the
errors of solubility start to account for a lot. Using an
NDVV analyser allows for totally heated sampling but
Infra red requires for the water to be removed from
the sample which presents the water condensate into
which the SO2 is dissolved.
The only practical solution is to allow adequate time
for the cal gas to equilibrate until it reads through the
sampling system the same as it does when
calibrating the analyser directly.
NO2
Most NO2 solubility problems do not exist as the
majority of analysers measure NO and this is less
soluble in water. NO2 is converted into NO in the
heated part of the sampling system or analyser.
The only requirement is to check the NO2 converter
efficiency periodically as described earlier.
Analysers which measure cold NOx and the NO2
converter is after any condensate removal device has
probably lost 50% of the NO2 in the condensator.
This, as previously stated, is only of real
consideration if the NO2 is a large constituent of NOx
in gas turbines.
HCL
This is perhaps the most tricky of all.
HCL is very soluble in water and to measure HCL
correctly the whole sampling train must replicate the
temperature of the stack gas. Thus heated lines,
filters, pumps, measuring cells etc. must be at least
190°C.
Again, though, the calibration gas is going to be very
dry coming from a gas cylinder at 250 bar initially,
when introducing HCL cal gas to the sampling point it
will “pull” all moisture out of the sample tubing etc.
and will dissolve the HCL in this moisture, producing
hydrochloric acid vapour.
After some time however this will equilibrate and
allow a stable reading on the analyser.
NH3
This largely follows the same as HCL.
Note
(1) As the introduction of soluble acid gases
into the sampling point introduces more questions
than answers, it is probably more effective to
introduce these gases directly to the analyser for gain
setting and allow adequate sampling period to obtain
a stable reading on the analysers. The introduction of
a dry cal gas to the sampling point will dry out the
sampling system and lose most of the cal gas and
then switching to sample mode reverses the whole
process until this has equilibrated.