AWA Article (P32 & P33) 3/22/04 4:38 pm Page 32

32 Air Monitoring

Ammonia Monitoring for

DENOX PROCESS
By Philippe Minghetti and Rachid Mouflih

The aim of this article is to look at the problems and some of the solutions
which have been developed for monitoring ammonia (NH3) in DeNOx process.
(O3) and nitrogen monoxide (NO) as shown in the
following equation: NO + O3 -> NO2 + O2 + light
The ammonia (NH3) must be first converted to NO
by a high temperature converter (about 800 °C). As
NO and NO2 might be present at high concentration in
the sample, the measurement is done alternatively
through and bypassing the converter to subtract the
NOx background. This operation introduces a delay of
a few seconds that is not compatible with short
response time that is needed, especially on motor
exhaust applications.
The chemiluminescence is subject to quenching
effect with the main combustion gases that are H20 and
CO2, producing a de-calibration of the instrument.

b) FT-IR

The FT-IR spectrometry is based on a Michelson

interferometer. The signal is recorded as a function of
the optical path difference between the fixed and the
movable mirror. Then a Fourier Transform is applied
from this interferogram to obtain the spectrum as a
function of wavelength.
The advantages of this technique are a higher spectral
resolution and a typically higher throughput in intensity
(no slit aperture required) compared to a classical IR
spectrometer.
The FT-IR is a powerful method but its inherent
high cost, long setting up and risk of interferences with
the main combustion gases as H20, CO, CO2, CH4,
BTX limit strongly his application for deNOx process.
Introduction (SNCR), also known as the thermal DeNOx process,
The European directive 2001/81/EC of 23rd October reduces NO by addition of ammonia in the flue gas c) NIR DLAS (Near Infrared Diode Laser Absorption
2001 has for objective to limit the emission of without the use of a catalyst. Ammonia is injected in the Spectroscopy)
pollutants and ozone precursors in order to improve high temperature region of the boiler to reduce NO to
the protection of the environment and human health. N2 thermally by the same overall reaction as occurs in The first and second overtones of the
National emission ceilings, taking the years 2010 and SCR shown above. rotational=vibrational modes of many gases molecules
2020 as benchmarks, has been fixed for every European Selective catalytic reduction systems have also generate absorption bands in the near infrared (0.8 – 3
countries concerning the nitrogen oxides (NOx), potential for reducing emissions of NOx in exhausts of um).
ammonia (NH3), sulphur dioxide (SO2) and volatile heavy-duty diesel vehicles. A solution of inexpensive The absorption spectroscopy is based on the beer-
organic compounds (VOC). urea stored on the vehicle is injected into the exhaust Lambert law on one of the absorption bands of the
The NOx, coming for more than 70% from upstream of the SCR catalyst. Urea when heated NH3 in the near infrared. The light is produced by a
combustion in vehicles and power plants, are liberates ammonia, initiating the SCR deNOx process laser diode with a current modulation to scan the
responsible for a very significant increase of the on the catalyst surface above 250 °C: selected absorption band.
respiratory diseases as bronchitis and asthma, especially One of the main difficulties is to select an absorption
for children and old people. (NH2)2CO + H2O -> 2NH3 + CO2 band free from other absorption bands coming from
A recent three-country European study [1] found that 4NO + 4NH3 + O2 -> 4N2 + 6H2O the combustion gases: H2O, CO, CO2, CH4, BTX.
air pollution causes 6% of all deaths, and thus kills many Long-term wavelength stability is one of the most
more people than traffic accidents. Therefore the process has to be controlled to keep the important problems on laser diode. It will require time
The nitrogen oxides NO and NO2 directly regulate ammonia slip in the exhaust [2]. to time a temperature adjustment by a highly qualified
O3 production rates and indirectly influence aerosol Ammonia plays an important role in the transport of operator to avoid failure.
abundances in the urban, rural, and remote acidifying pollutants and is also involved in formation of As the absorption typically drops by an order of
troposphere. Emissions of NOx are thus responsible secondary particulate matter aerosols in the magnitude for every higher overtone, a multi-pass cell is
for the major components of photochemical smog. atmosphere. generally necessary to achieve a correct sensitivity, that
Ammonia may also give formation to ammonium increases the cost of the instrument as well as the
salt that might plug equipment downstream of the response time as the volume of a multi-pass cell is
DeNOx process SNCR process. significantly higher than a single pass cell.
Selective catalytic reduction (SCR) is a well developed Some of these ammonium salts are hygroscopic and Moreover, particulates in the gas limit strongly the
and widely used method for reducing NOx emissions in corrosive like ammonium bisulphate (NH4HSO4). maximum acceptable optical path.
the flue gas of a stationary combustor. The process
involves the reduction of NO (and NO2) to N2 with Scoop of existing methods for d) FT-UV (new method)
approximately stoichiometric amounts of ammonia ammonia monitoring
over a catalyst bed. The overall reaction is: a) Chemiluminescence with NH3 converter The measurement principle is based on the UV
4NO + 4NH3 + O2 -> 4N2 + 6H2O The chemiluninescence is based on the light emission absorption spectrum of the ammonia gas (NH3) in the
The selective non-catalytic reduction process coming from the chemical reaction between ozone UV range (figure). The periodic structure of the

IET March/April 2004

AWA Article (P32 & P33) 3/22/04 4:39 pm Page 33

Air Monitoring 33

Conclusion
The FT-UV method appears to be the most suitable method for ammonia monitoring
on deNOx process, whatever for power generator or motor benches. Ultra-fast
response time, high selectivity, no risk of interference with the major emission gases as
H2O, CO, CO2, CH4, moderate cost and very low maintenance are the main
advantages of this technology.
Real applications of this technology on heavy-duty vehicle exhaust bench have
confirmed theses advantages.
The possibility to monitor NH3 together with NO/NO2 on the same instrument
offer to the user a complete tool for deNOx process control and/or optimisation.

Bibliography
[1] Künzli, N. et al. Public health impact of outdoor and traffic-related air pollution:
a European assessment. Lancet, 356: 795–801 (2000).
absorption bands coming from the different levels of rotational energy of the gas [2] CONCAWE, report no. 99/62, Potential of exhaust after treatment and
molecules is analysed by performing a Fourier Transform on the absorption spectrum. engine technologies to meet future emissions limits
The main problem is to compute the spectrum is real time (that means in less than
a second) that usual microprocessors are unable to do. Hopefully, high speed DSP [3] Gunther, Barkley, Kolbezen, Blinn, Staggs - University of California, Vol28, no12, 1956.
Quantitative Microdetermination of Gaseous Ammonia by Its Absorption at 204.3 nm
(Digital Signal Processor) recently appeared on the market are able to perform this kind
of calculations in a few tens of milliseconds.
The selectivity is guaranteed by the typical periodic structure of ammonia, different

AUTHOR
from any other gases. Typical measuring ranges are from a few ppm to tens or Mr Philippe Minghetti and Mr Rachid Mouflih
hundreds of ppm.
Other gases as NOx may be measured simultaneously by the spectrograph for a Awa Instruments SAS
low additional cost. 15 Chemin du Vieux Chene, F-38240 Meylan ZIRST – France
The fully solid-state measuring system is represented on the figure below. A xenon Tel +(33) 476 41 86 39 Fax +(33) 476 41 92 27
flash mode lamp having a 10 years typical lifetime is used as UV light source.
e-mail: [email protected]
A second microprocessor takes in charge all the auxiliary functions: measurement
www.awa-instruments.com
display, trend graph, 4-20 mA output, data logging, checking, zeroing, calibration.

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