IMPACT ASSESMENT OF NOx EMISSIONS FROM CEMENT INDUSTRY

Formation of NOx in cement industry

Nitrogen oxides (with a share NO about 95% and N2O about 5%) are the key pollutants emitted
into the atmosphere during cement production. They are majorly produced in clinker formation.
here are three ways of nitrogen oxides formation during the Portland cement clinker baking
thermal nitrogen oxides (thermal NOx); fast nitrogen oxides (fast NOx) and fuel nitrogen oxides
(fuel NOx).

1.1.Thermal NOx

Thermal NOx can be formed at high temperatures (>1200оС) and high concentration of oxygen
during oxidation of atmospheric nitrogen with oxygen during combustion. Thermal NOx only
consists of Nitrogen monoxide (NO) as it is formed in flame zone of combustor. With an increase
in the flame temperature and the excess air ratio in the furnace, the amount of generated thermal
NOx increases. Thermal NOx can be mainly formed by burning gaseous fuels (natural gas and
liquefied petroleum gas) and fuels that do not contain nitrogen-containing substances.

1.2. Fast nitrogen oxides

Fast NOx can be formed in a burning fuel flame by complex reactions of radical interaction СН
with nitrogen N2 with HCN formation, which then is quickly disintegrated into NOx, CO2 and
H2O. Majorly N2O with small percentage of NO is formed during this step. (Note: exact percentage
is not given in literature) Content of fast NOx depends on the shape and temperature profile of the
flame and increases during the combustion of enriched mixtures and during low-temperature
combustion, reaching 25% of the total amount of the formed nitrogen oxides.

1.3.Fuel NOx

Fuel NOx can be formed from nitrogen-containing compounds that are part of solid and liquid
fuels, especially coal. NOx formation mechanism consists converting nitrogen-containing fuel
compounds into ammonia NH3 and HCN followed by additional oxidation to NOx. Here NO is
major product which when released in atmosphere can convert into NO2.

So overall in above 3 processes 20% NOx are released as thermal NOx, 5% as fast or prompt NOx
and 75% as fuel NOx.

Impacts of NOx on human health

Breathing air with a high concentration of NO2 can irritate airways in the human respiratory
system. Such exposures over short periods can aggravate respiratory diseases, particularly asthma,
leading to respiratory symptoms (such as coughing, wheezing or difficulty breathing), eyes and
heart diseases. Longer exposures to elevated concentrations of NO2 may contribute to the
development of asthma and potentially increase susceptibility to respiratory infections. People
with asthma, as well as children and the elderly are generally at greater risk for the health effects
of NO2. Nitric oxide (NO) spreads to all parts of the respiratory system because of its low solubility
in water. Nitrogen oxides diffuse through the Alveolar-cells (epithelium) and the adjacent capillary
vessels of the lungs and disrupt the Alveolar structures and their function in lungs NO2 along with
other NOx reacts with other chemicals in the air to form both particulate matter and ozone. Both
of these are also harmful when inhaled due to effects on the respiratory system.

Figure 1: Effects of Nitrogen dioxide on human health

 Impacts of NOx on Environment

The effect of NOx on environment are as follows

 NO2 and other NOx interact with water, oxygen and other chemicals in the atmosphere to
form acid rain. Acid rain is actually nitric acid which harms sensitive ecosystems such as
lakes and forests.
 Additionally, NOx deposition in the oceans provides phytoplankton with nutrients,
worsening the issue of red tides and other harmful algal blooms.
 NOx gases play an important role in the formation of smog, producing the brown haze.
 During exposure to UV rays in sunlight and heat, NOx molecules interact with volatile
organic compounds (VOC) and form ground-level (or tropospheric) ozone (O3). Ozone at
the ground level is a serious pollutant, unlike the protective ozone layer much higher up in
the stratosphere.

Figure 2: Effects of NOx on environment

 Technologies for NOx Reduction

NOx can be reduced by various methods among which stage combustion, selective catalytic and
non-catalytic reduction are proven more effective.
4.1. Staged fuel combustion
Staged fuel combustion is used in dry-process cement kilns. The first combustion stage takes place
in a rotary kiln under optimal clinker firing conditions. The second combustion stage is in the
burner at the entrance to the furnace, where the reducing atmosphere is formed. This leads to the
decomposition of some of the nitrogen oxides accumulated in the firing zone. At a high
temperature, NOx reduction reaction to elemental nitrogen takes place in this zone. At the third
stage, fuel and tertiary air are fed to the calciner, which also results in a reducing atmosphere. At
the same time, the number of NOx, formed during fuel combustion, is reduced as well as the
amount of NOx, coming into the kiln from the outside. At the fourth final stage, the remaining
tertiary air is fed to the top of the system for residual combustion.
4.2. Selective non-catalytic reduction
The technology of selective non-catalytic reduction of nitrogen oxides includes injection of an
aqueous solution of ammonia into the flue gases (up to 25% NH3) or aqueous solutions of ammonia
or urea compounds for reduction of NO till N2 formation. To ensure the sufficient contact time of
the reducing agent with the flue gases, the optimum temperature should be 830 - 1050оС.

4.3. Selective catalytic reduction

In SCR technology nitrogen oxides are reduced to N2 by means of NН3 and catalyst at a
temperature of about 300-400оС. SCR technology is used much less frequently, which is associated
with a high cost (about 10 times higher than SNCR) and limited catalyst life.
 Table 1: Comparison of technology options to reduce NOx emissions

Sr. Parameter Staged combustion Selective non Selective catalytic reduction

# catalytic reduction

1 General Very cost effective Cost effective, Expensive and complex

Technology sufficiently high medium / high NOx but effective technology
assessment potential for NOx emissions reduction with low NOx (~ 20 mg/m3)
emissions reduction potential and NH3
emissions potential
2 Applicability For dry and wet For dye process For dye process plants
processing plants Requires wide space for
production Can be combined equipment
plants with an with staged
upgraded combustion
kiln
Most effective for
kilns with heat
exchanger, calciner
and tertiary duct.
Built-in calciner
required
4 Investment Low (can be high for Average Very High
cost complex
modification
projects)
5 NOx emissions 10–50% 30–90% 43–95%
reduction rate

References

1. https://www3.epa.gov/ttncatc1/dir1/cement_updt_1107.pdf
2. Kim, Ji-Hyeon, et al. "Reduction of NOx Emission from the Cement Industry in South
Korea: A Review." Atmosphere 13.1 (2022): 121
3. Boningari, Thirupathi, and Panagiotis G. Smirniotis. "Impact of nitrogen oxides on the
environment and human health: Mn-based materials for the NOx abatement." Current
Opinion in Chemical Engineering 13 (2016): 133-141.

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