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TI-A-Guide To Combustion Optimization 1 PDF
TI-A-Guide To Combustion Optimization 1 PDF
TI-A-Guide To Combustion Optimization 1 PDF
“A complex sequence of exothermic chemical reactions Sulphur oxides (SO2), nitrogen oxides (NO, NO2) plus nitrogen.
between a fuel and an oxidant accompanied by the
production of heat or both heat and light” The term hydrocarbon fuels is not restricted to the traditional
fossil fuels of coal, oil and gas, but also includes biomass
For the purposes of this guide, combustion can be defined as (encompassing anything from waste wood right through
the oxidation of a fuel, mainly hydrocarbon, for the purpose of to waste water sludge), waste to fuel products (such as
producing useful heat. shredded motor vehicle tyres), waste products from industry
(black liquor from pulp and paper, industry, offgas from
A simple example of this is methane (CH4). petrochem processes and the steel industry, etc). This list is
only a sample of the possible fuel types.
Methane (the fuel) + oxygen, produces carbon dioxide + water
+ heat, or: As the basic principles of combustion apply equally to any
of these fuels, for this discussion, the fuel type will be
CH4+2O2 ‡ CO2 + 2H2O + heat largely ignored.
Whilst heat released from the combustion process can Based on empirical data, it uses the net exhaust temperature,
approach 100 per cent efficiency, the transfer of this heat a fuel constant calculated from the hydrogen/carbon ratio
to raising steam introduces losses. To ensure optimum of the fuel and the excess oxygen measurement of the
combustion efficiency, the amount of excess air supplied exhaust gas:
needs to be closely monitored and controlled. Continuous
monitoring of the exhaust gases is therefore required, with Efficiency = 100 - (K(T1-T2) / (20.8 - % O 2)
the oxygen value being the preferred measurement for
combustion control.
NOx emissions are created in three main ways: In addition, the volume of CO2 in flue gas varies according
1. Thermal NOx – generally produced during the combustion to the type of fuel in question, whereas the percentage of
of both gases and fuel oils, thermal NOx is produced as a oxygen remains fairly consistent, with a three to nine per cent
result of nitrogen and oxygen in the combustion air supply concentration in flue gases in the most common fuels.
combining at high flame temperatures
2. Fuel NOx – this occurs when excess oxygen in the In the early 1940s, paramagnetic oxygen measurement
combustion air combines with nitrogen in the fuel. It is only became the preferred method of measurement. This method
a problem with fuel oils with a high nitrogen content was based on the magnetic properties of oxygen and gave a
3. Prompt NOx – this type of NOx is formed during the initial, more meaningful measurement of excess oxygen. However,
low temperature stages of combustion and, as such, the sample still had to be extracted in the same way as a
is largely insignificant CO2 measurement.
Of these the most significant is thermal NOx.
Air
-ve mV +ve
introduction of in-situ zirconia oxygen sensors in the late
1960s. Capable of being inserted into the flue or furnace,
these sensors enabled operators to achieve an in-situ
measurement, thereby eliminating the drawbacks associated Reference air
with extractive systems.
Outer
Zirconia oxygen sensors – how they work electrode
Inner
Although zirconia oxygen sensors are a relatively recent
electrode
innovation, the understanding of the operation of zirconia
as a solid electrolyte goes back before 1900. It was
electrochemical research by German physicist Walther
Nernst that identified the physical properties resulting in
the publication of results in 1899 in the Journal ‘Zeitschrift
Zirconia
für Electrochemie’. Nernst discovered that the oxide of the tube
element zirconium called zirconia (ZrO 2) was conductive
to oxygen ions when a difference of oxygen concentration
existed across zirconia, when heated to temperatures of Process gas
over 600°C (1,112°F).
A basic sensor consists of a thin piece of zirconia material. This potential difference provides a suitable mV signal that
The electrical connection to the sensor is provided by can be simply measured, using appropriate electronics, which
applying a coating of porous platinum to the two opposite can then display percentage oxygen concentration in the
faces. A supply of air is supplied to one face of the sensor as process gas.
a reference gas to provide a constant oxygen concentration.
The process gas, to be measured, is then presented to the In practice, the sensor is constructed in the shape of a
opposite face of the sensor. The platinum acts as a catalyst, thimble (a small tube with a closed end) made from zirconia.
in the presence of oxygen gas, where free electrons enable Yttria (yttrium oxide) is added to the zirconia material to
the conversion of molecular oxygen to oxygen ions. These improve its electrolyte properties, in providing greater mobility
ions are mobile and can migrate through the solid to oxygen ions. It also provides good mechanical strength and
zirconia electrolyte. resistance to thermal shock.
When the concentration of oxygen is in equilibrium on both Net vs. Gross / Wet vs. Dry readings
sides of the sensor, migration of the oxygen ions through the Where a portable oxygen analyzer is used to confirm the
zirconia, is zero. Where there is a difference in concentration, calibration of an in-situ oxygen analyzer, operators will often
i.e. when the oxygen in the process gas falls, the migration notice a discrepancy, with the portable analyzer showing a
of the oxygen ions will increase in order to re-establish higher reading than the measurement shown by the zirconia
equilibrium. The reaction at the two electrodes will therefore based oxygen analyzer.
differ, generating a corresponding potential difference.
The difference between the two readings is due to the
E = RT/4F LN P1/P2 difference between ‘net’ and ‘gross’ oxygen measurement
Where E – is the cell potential and the difference between ‘wet’ and ‘dry’ oxygen
R – is the universal gas constant measurement.
(8.314472 J K -1 mol-1)
T - is the absolute temperature in degrees kelvin
F – is the Faraday constant
(F = 9.6485309×104 C mol-1)
P1 – is the reference oxygen partial pressure
P2 – is the sample oxygen partial pressure
This sample must then be filtered and cooled. The cooling The table on the next page illustrates the expected errors if
process will remove most of the water vapor from the sample the sample point is below atmospheric pressure by 10 mbar.
before it is presented to the sensor. So this type of analyzer
measures the oxygen content with most of the water vapor
removed. The result is an oxygen reading, which is higher
than the ‘hot’ and ‘wet’ reading obtained from the in-situ
oxygen probe.
Examining column four in the table shows that the mV error The alternative method is to compensate for the difference
is a constant offset. This shows that calibration of the probe in pressure between the reference air and the sample.
whilst in-situ, with the process running at normal fixed This is simply done by measuring the instantaneous sample
pressure, will compensate for the difference in pressure pressure, input the data into the oxygen analyzer, or the
between the sample and the sensor reference air. plant’s DCS, which can then automatically adjust the
oxygen reading for the difference between atmospheric
An application that in-situ zirconia based analyzers cannot pressure and the sample pressure.
easily handle is where the process pressure is not only
significantly different to ambient pressure, but large variations E = RT/4F LN (Preference * O2 reference) / (Psample * O2 sample)
are also experienced. When both the process oxygen
concentration and process pressure changes, it is impossible Where: E – is the cell potential
to ascertain whether the change in the display of the oxygen R – is the universal gas constant
analyzer is attributable to a change in the process pressure or (8.314472 J K -1 mol-1)
to a change in the oxygen concentration. T – is the absolute temperature in degrees Kelvin
F – is the Faraday constant
There are two possible solutions in use to overcome this (F = 9.6485309×104 C mol-1)
situation. The most common is to balance the reference air Preference – is the reference absolute pressure
supply pressure to that of the process. Psample – is the sample absolute pressure
O2 reference – is the reference oxygen concentration
O2 sample – is the sample oxygen concentration
Certain other gases, commonly present in flue gas, will be If the user knows the concentration of the interfering
inert towards the zirconia oxygen electrode and produce combustible gases then it is possible for them to make the
no error. These include nitrogen, argon, carbon dioxide and correction to the reading manually by calculation. There
water vapor. is no facility in our range of zirconia monitors to make this
correction automatically. Worked examples are shown on the
following page.
The ratios, and hence the errors, for sulphur dioxide and
hydrogen sulphide may not be precisely according to the
combustion equations shown. The oxidation of sulphur
dioxide may not go to completion in the timescale of passing
through the catalytic electrode and some of the sulphur
dioxide from the hydrogen sulphide oxidation may oxidize
further to sulphur trioxide.
Germany UK Notes:
Ref: AD-Combustion-Guide-EN-Issue1
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