Proceedings of the 6th International Conference on Process Systems Engineering (PSE ASIA)

25 - 27 June 2013, Kuala Lumpur.

Kinetic Model for Ammonia and Urea Production

Processes
Z. Umair†,, P. Balasubramanian†, and M. Shuhaimi†

† Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri

Iskandar, 31750 Tronoh, Perak, MALAYSIA

Abstract

The production of urea is important in an agricultural sector as a fertilizer. It is

manufactured from ammonia and carbon dioxide. Presently, the synthesis of ammonia
and urea take place separately in a fertilizer industry. Integration of ammonia and urea
synthesis plants is indispensable to maximize yield of urea and to minimize the energy
cost. Thus, in the work, kinetic models for ammonia and urea reactors are presented and
simulation was performed. The performance of ammonia and urea synthesis reactors
was carried out by varying temperature and pressure and satisfactory results were
obtained.

Keywords: kinetic; ammonia; urea; energy saving; reaction coupling; plugflow reactor

1. Introduction

Ammonia is an important raw material for the production of urea in an agricultural

sector. The current ammonia and urea productions are done separately. Ammonia is
produced from nitrogen and hydrogen feedstocks in multibed reactor at the conversion
of only around 20%. Urea is further produced by reacting ammonia with carbon dioxide
in a downstream urea reactor. Both reactions are highly exothermic and their operating
conditions are different. Higher temperature and pressure (500°C and 300 atm) are
essential for the ammonia production while urea is produced at more moderate
temperature (180°C) and at high pressure (236 atm). The integration of two processes
are important in order to improve the yield of urea as well as energy and cost saving.
Kinetic model for an integrated ammonia-urea production process is not well
established so far, and the model is essential for better understanding of an integrated
process. Therefore, it is proposed to develop a kinetic model for an integrated ammonia-
urea production process. In the following, the kinetic model form the two systems are
described.
326 Z. Umair et Al

Figure 1: Schematic diagram of the integrated ammonia-urea production plants

2. Kinetic Modeling

2.1. Kinetic Model for Ammonia Synthesis Reactor

The reaction involved for an ammonia synthesis reactor is

(1)
The mass balance equation for the conversion of nitrogen along the length of an
ammonia reactor can be represented as [Dhasti, 2006]

(2)

where X is the conversion of nitrogen along the z-axis. The initial molar flowrate of

nitrogen is expressed as , and is the effectiveness factor.

The reaction rate for the formation of ammonia is obtained from modified Temkin
equation [Dyson & Simon,1968]

(3)

Where , A = 8.849x , E = 40765 , and α = 0.5.

is equilibrium constant, a is activity of the component and α is constant. The

correlations , , and ( ) are available elsewhere [Dyson and
Simon, 1968].

2.2. Kinetic Model for Urea Synthesis Reactor

The reaction schemes for urea synthesis are,

(4)

(5)
Kinetic Model For An Integrated Ammonia-Urea Production Process 327

And the overall reaction will be,

(6)

The development of urea synthesis model is based on the reaction rate equation of the
formulation of Urea, Ammonium Carbamate and Carbon Dioxide along the reactor
length [Piotrowski et al. 1998]. The conversion of reaction (4) and (5) will be denoted
as and while the overall conversion as . These will give,

(7)

(8)

(9)

The total for initial flowrate, will be the sum of the initial flowrate of the individual
components. For the flowrate of each component at any point, the following equations
will be used,

(10)

(11)

(12)

(13)

(14)

Where flowrate of urea is denoted as , carbamate as , carbon dioxide as

ammonia as and water as . The total flowrate, of the components will be the
sum of all individual flowrate.

The rate of disappearance of carbon dioxide, is as given by,

(15)

where is kinetic for the forward reaction in equation (4) and is equilibrium
constant. The rate of formation of carbamate, and urea, are,

, and (16)

(17)
328 Z. Umair et Al

where represent the forward reaction in equation (5) and is the equilibrium
constant. The mole balance equations for the species, urea, carbamate and carbon
dioxide in an ideal plugflow reactor are,

(18)

(19)

(20)

where A is the area of the reactor.

3. Results and Discussion

Simulation of an ammonia synthesis process is carried out using MATLAB and the
mole fraction of nitrogen, hydrogen and ammonia along the length of an ammonia
reactor at different operation conditions are determined.

The initial molar flowrate of nitrogen used is 10,000 , the rate of H2/N2 is 3, the
effectiveness factor is 1 and the area of the reactor A is 1.1310m2. Figure 2 shows the
results obtained for various temperatures at constant pressure of 150atm.

(a) (b)

(c) (d
Figure 2: Effect of temperature on the product distribution in ammonia reactor. (a)
350°C, (b) 400°C, (c) 450°C and (d) 500°C.
Kinetic Model For An Integrated Ammonia-Urea Production Process 329

(a) (b)

Figure 3: Effect of pressure on the product distribution in ammonia synthesis reactor.

(a) 150atm and (b) 300atm

The yield of ammonia increases with an increase in temperature from 350°C to 500°C at
a constant pressure of 150atm in an ammonia synthesis reactor (see figure 2).
Furthermore, the yield of ammonia is increased with increased on pressure from 150atm
to 300atm at a temperature of 450°C as shown in figure 3.

Similarly, simulation of urea synthesis process is carried out using MATLAB and the
mole fraction of ammonia, carbon dioxide, ammonium carbamate, urea and water along
the length of an urea reactor at different operation conditions are determined. The initial
molar flowrate for carbon dioxide and ammonimum carbamate are 2,000 and 100
respectively. For forward and backward reaction, the equilibrium constants used are 2.5
and 65.6 and the activation energies are 139500 and 98500 J/mol respectively. The pre-
exponential factors of the reaction are 2.07x1010 and 9.00x1011 s-1. Figure 4 shows the
effect of temperature on the yield of urea in a urea synthesis reactor at a constant
pressure of 247atm.
330 Z. Umair et Al

(a) (b)

(c) (d)
Figure 4: Effect of temperature on product distribution in an urea synthesis reactor.
(a)443°C (b) 463°C (c) 473°C (d) 483°C

Here, the mole fraction of urea increases with the increase in temperature from 443 to
453°C.

The integrated kinetic model for simultaneous synthesis of ammonia and urea is not
presented in this paper and this will be the future scope of the present study.

4. Conclusion
In this work, the kinetic models for ammonia synthesis and urea synthesis reactor were
developed and simulation of both process were carried out. Both temperature and
pressure have significant effect on the yield of ammonia as well as urea in the
standalone reactors.

References
Dashti, A., Khorsand, K., Marvast, M. A., & Kakavand, M. (2006). Modeling and Simulation of
Ammonia Synthesis. Petroleum & Coal, 15-23
D.C. Dyson and J.M. Simon. “A Kinetic Expression with Diffusion Correction for Ammonia
Synthesis on Industrial Catalyst”, Ind. Eng. Chem. Fundamental, Vol. 7, No. 4, pp. 605, 1968.
Piotrowski J., Kozak, R., Kujawska, M. (1998). Thermodynamic Model of Chemical and Phase
Equilibrium in the Urea Synthesis Process, Chemical Engineering Science, Vol. 53, No. 1,
pp.183-186.