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A Practical Solution to Abate Emission of Ammonium Nitrate and Ammonia

during Prilling and Granulation Processes

Article · January 2012

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 International Journal of Modern Chemistry, 2012, 2(2): 57-63
International Journal of Modern Chemistry ISSN: 2165-0128
Journal homepage: www.ModernScientificPress.com/Journals/IJMChem.aspx Florida, USA
Article
A Practical Solution to Abate Emission of Ammonium Nitrate
and Ammonia during Prilling and Granulation Processes
Ahmet Ozan Gezerman *

Department of Chemical Engineering, Faculty of Chemical-Metallurgical Engineering, Yildiz

Technical University, Istanbul, Turkey

* Author to whom correspondence should be addressed; E-Mail: ahmet_ozan@yahoo.com; Tel.: + 90

532 653 85 05; +90 536 341 69 59.

Article history: Received 18 June 2012, Received in revised form 12 July 2012, Accepted 13 July 2012,
Published 15 July 2012.

Abstract: As the production of chemical fertilizers is increasing, controlling the emissions

from the manufacturing process is a significant problem that manufacturers need to solve.
Until now, the various proposed solutions, based on chemical methods, have had limited
yields. In this study, we propose a more practical and effective technique, based on
chemical precipitation, for the abatement of ammonia emission as well as the emission of
other ammonia-based chemicals produced during the prilling and granulation processes in
the manufacture of fertilizers.

Keywords: emission gas; ammonia; fertilizer; granulation; prilling; chemical precipitation.

1. Introduction
The emission of ammonium nitrate and ammonia during the processes involved in the
manufacture of fertilizer is a problem that engineers have worked to solve with the support and
encouragement of governments [1]. The fertilizer manufacture process has to be kept in mind and the
physical and chemical conditions of the process need be considered. Furthermore, the energy
requirements of the abatement system should also be evaluated [2].
A number of solutions to this problem of abatement have been proposed [3]. One of these
solutions is to feed the emission gases back into the reaction process for fertilizer manufacture. Other
solutions include injecting these emission gases into an alkaline steam during the reactions for the

Copyright © 2012 by Modern Scientific Press Company, Florida, USA

Int. J. Modern Chem. 2012, 2(2): 57-63 58

manufacture of fertilizers [4]. These systematic solutions are reproducible [5]. However, adding filling
materials that can dilute the fertilizer solution while maintaining the conditions for the fertilizer
manufacturing reaction is not a commonly used approach [6]. Furthermore, these solutions have
generally not been widely implemented as they are limited by the physical conditions prevailing in
existing manufacturing facilities. Thus, a new process needs to be designed that can be used in existing
factories [7]. Furthermore, for the prilling and granulation processes in the manufacture of fertilizers,
parameters such as pressure and temperature are of prime importance and need to be kept constant [8].

2. Materials and Methods

2.1. Experimental Conditions

It is assumed that the factory where the fertilizer is being produced has a capacity of 100 t/h,
has cooler motors with a power rating of 40 kW for the prilling and granulation processes, and the
volume of air in the cooling towers cane is 150.000 m3 [9]. Then, for a typical fertilizer production
process, as per the probable reaction of calcium ammonium nitrate, the rate at which gases are emitted
during prilling will be 150.000 m3/h [10]. The mixture of the emission gases (1) is listed in Table 1
[11,12].

Table 1. The mixture of the emission gases

Emitted gas Rate (kg/h) Percentage in mixture (%)
H2O 3,000 2
(NH4)2SO4 30 0.02
NH4NO3 120 0.08
Ca(NO3)2 0.00375 0.0000025
CaCO3 0.00375 0.0000025

The average molecular weights of the emission gases can be calculated by using these
percentage values. These calculations will aid in determining the vapor pressures of the gases exiting
the cooling towers.
The molecular weight of air is (0.79 × 28) + (0.21 × 32) = 22.12 + 6.72 = 28.84 g/mol. The
molecular weight of the emission gases at a chosen point is given by
(18 × 2%) + (80 × 0.08%) + (132 × 0.02%) + (102 × 0.0000025%) + (100 × 0.0000025%) +
28.84 × 0.979 = 28.23436+ 0.4504 = 28.68476 g/mol.
According to the ideal gas equation, P × MW = d × R × T,

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Int. J. Modern Chem. 2012, 2(2): 57-63 59

where P is the gas pressure, Mw is the molecular weight, d is the density of the gas emitted, R is the
universal gas constant, T is the temperature.
P = 1.145× 0.082 × (273+50)/28.68476 = 1.057 atm.
Into these emission gases, when water is added over 1 h to condense the 50% of water present
in the emission gas,
m = 2.08717 × 10 –2 – 2.21315 × 10-4 Tw + 2.0416 × √θ (e-4217.96/Tw) + mo
where mo is the initial amount of emission gases at the outlet of the prilling tower (1), Tw is the dew
point of water at the spray head, m is the amount of water after condensation at the final point (2), θ is
the diffusion coefficient of the emission gases at 50 °C (for this particular mixture of emission gases).
Using this formula, we can find the amount of water present in the emission gas mixture [13].
The same calculation can be made for the emission gases at 50 °C (Tw). The result obtained showed
that, given the stoichiometric ratios with the condensed gas, the mass of the emitted gases is 44% of
the initial mass. After the emission gases, which are 44% of the initial mass, condense, the materials
remaining in emission gases are given below. After condensation (2), the emission of air at a rate of
150.000 m3/h, and emission gas mixture are given in Table 2.

Table 2. Emission gas mixture after condensation

Gas material in emission Amount (kg/h) Percentage in mixture (%)
H2O 1,320 0.88
(NH4)2SO4 13.2 0.0088
NH4NO3 52.8 0.0352
Ca(NO3)2 0.00165 0.0000011
CaCO3 0.00165 0.0000011

After this chosen point (2), the molecular weight of the emission gases that condense and are
44% of the initial mass are given as follows:
(18 × 0.88%) + (80 × 0.0352%) + (132 × 0.0088%) + (102 × 0.0000011%) + (100 ×
0.0000011%) + 28.84 × 0.99076 = 28.77169 g/mol.
P 2 × MW = d × R × T
P2 = 1.145 × 0.082 × (273 + 35)/28.77169 = 1.005 = approximately 1 atm.
Because pressure P1 is greater than pressure P2, the value of P2 will not influence the value of
P1 at the exit of the prilling tower.
With these pressure values, after the abatement of the emission of gases after condensation, the
solidification of harmful chemicals will be possible by chemical precipitation. Generally, these

Copyright © 2012 by Modern Scientific Press Company, Florida, USA

Int. J. Modern Chem. 2012, 2(2): 57-63 60

methods are used for the removal of heavy metals. The same reactions occur during these removal
methods as well. These methods are based on differences in the solubilities of the chemicals at
different pH levels. Reactions that should be known here are as follows:
Reaction for the precipitation of ammonium sulfate by FeCl3:
3(NH4)2SO4+ 2FeCl3 6NH4Cl + Fe2(SO4)3
Reaction for the precipitation of ammonium nitrate (with a pH value of 9) by adding NH4OH:
NH4NO3 + NH4OH NH3 (gas) + NH4NO3 + H2O
Reaction for the precipitation of Ca(NO3)2 (with a pH value of 12) by adding NH4OH:
Ca(NO3)2 + NH4OH NH3 (gas) + Ca(NO3)2 + H2O

3. Results and Discussion

In production processes that result in the emission of excessive amounts of ammonia and
ammonium nitrate, such as the manufacturing of fertilizers, the abatement of the emission of chemicals
to the environment needs alternative solutions, especially when water treatment is concerned. As the
need for fertilizers increases, so does the amount of gases emitted during the production of fertilizers.
A number of solutions specific to the mixture of gases emitted have been proposed. Nevertheless, they
have yielded similar results.
In the method proposed by us, we initially consider the applicability of the method to existing
factories and economic conditions. Furthermore, we do not propose the use of any extra equipment or
reactor, ensuring that the precipitation is performed using raw material already available in the factory.
Air is used to cool the product in the proposed process. Air works as a kind of catalyst, for the
discharge from the precipitation tanks that are shown in Fig. 1. It also condenses a lot of the water
present in the emission gas mixture by decreasing the dew point of water. The amount of water that is
introduced via the water spray is not a factor that affects the value of the pH in precipitation tanks (Fig.
2). Hence, this way is possible to remove the emission gases and harmful chemicals from the system.

Copyright © 2012 by Modern Scientific Press Company, Florida, USA

Int. J. Modern Chem. 2012, 2(2): 57-63 61

Figure 1. Outlet for emission gases from the prilling tower.

Limiting factors such as the potential and kinetic energies of prilling and granulation processes
are also considered. The effect of such factors is case, which is seen on the movement of the discharge
gases to the wastewater region through the flow in the system. The flow is expressed as the pressure
difference at the point where the movement of emission gases begins. The pressure in the system
decreases until the precipitation tanks and makes the movement of the gas easy. The discharge of
wastewater from the system discharge point occurs under vacuum.
Other solutions are available for similar processes in the industry and include methods such as
feeding the emission gases back into the fertilizer manufacture reactor. However, suitable materials
that can be used to dilute the fertilizer solution are not available in the amounts needed, and therefore,

Copyright © 2012 by Modern Scientific Press Company, Florida, USA

Int. J. Modern Chem. 2012, 2(2): 57-63 62

it is not possible use this proposed solution of feeding the gases back into the reaction. Furthermore,
the temperature of the emission gases needs to be considered in the solution based on the feeding of
the gases back into the reactor. Feeding the gases back into the system to ensure the removal of a
greater amount of steam from the emission gases also affects the economy of process. Therefore, the
method proposed by us does not incorporate the step of feeding the gases back into the reactors.

Figure 2. Chemical precipitation tanks (Tops of the tanks are covered by perforated filter fabric).

4. Conclusions

It is important to minimize the emission of gases during the manufacture of fertilizers. Towards
this end, governments actively encourage manufacturers to invest in the development of processes that
can help minimize the emissions. We have proposed and studied a method of abating the emission of
gases by chemical precipitation. We have preformed calculations to ensure the physical, chemical and
thermodynamic stability of the process while obtaining the granulated product from the fertilizer
solution. It is also shown that this method can be easily used with other chemical systems for the
precipitation undesirable components.

References

[1] Ammonium Nitrate Manufacturing Industry: Technical Document, EPA-450/3-81-002, U. S.

Environmental Protection Agency, Research Triangle Park, NC, 1981.

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Int. J. Modern Chem. 2012, 2(2): 57-63 63

[2] Ammonium Nitrate Production Facility Expansion, Kwinana, Environmental Protection Authority
Perth, Western Australia Bulletin 1182, 2005.
[3] Control and Pollution Prevention Options for Ammonia Emissions, Control Technology Center,
Air and Energy Engineering Laboratory, 1995.
[4] Pye, H. O. T.; Liao, H.; Wu, S.; Mickley, L. J.; Jacob, D. J.; Henze, D. K.; Seinfeld, J. H. Effect
of changes in climate and emissions on future sulfate-nitrate-ammonium aerosol levels in the
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[6] Ammonium Nitrate Production Facility Greenhouse Gas Abatement Program (incorporating
nitrous oxide emissions improvement plan), Version 8, 2011. [Online]:
http://www.csbp.com.au/Media/Environment/greenhouse_gas.aspx.
[7] Lagana,V.; Zardi, U. Process for recovering powders obtained from apparatuses used for treating
liquid or solid materials. United States Patent, 4,217,114, 1980.
[8] Williems, M.; Klok, J. Method for making urea prills and urea prills obtained by applying this
method. United States Patent 4,390,483, 1983.
[9] Processes For Fertilizer Production, Mineral Fertilizer Production and The Environment,
Technical Report, United Nation Publications, The Fertilizer Industry's Manufacturing Processes
and Environmental Issues, No 26 - Part 1, Vienna, 1996.
[10] Harry, L.; Mahl, J.; Franklin, D. Process for prilling ammonium nitrate. United States Patent
4,076,773, 1983.
[11] Estimates from Fertiliser and Plants Fertiliser, B1010-1, Cultures with Fertilizers, 1999.
[Online]: http://www.eea.europa.eu/publications/Emepcorinair/group10.pdf.
[12] Nitrogenous Fertilizer Plants, Pollution Prevention and Abatement Handbook, World Bank
Group, 1998. [Online]: http://www.ifc.org/ifcext/enviro.nsf/content/environmentalguidelines.
[13] Kayisoglu, B.; Esen, M. Nem absorbsiyon ozelliklerinin saptanması uzerine bir arastırma. J.
Tekirdag Agric. Faculty 2007, 4: 137-141.

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