A DUAL APPROACH FOR MODELLING AND OPTIMISATION OF INDUSTRIAL UREA

REACTOR: SMART TECHNIQUE AND GREY BOX MODEL

Sohrab Zendehboudi,1 * Gholamreza Zahedi,2 Alireza Bahadori,3 Ali Lohi,4 Ali Elkamel1 and Ioannis Chatzis1
1. Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1
2. Chemical & Biological Engineering Department, Missouri University of Science & Technology, Rolla, Missouri 65409
3. School of Environment, Science and Engineering, Southern Cross University, Lismore, NSW, Australia
4. Department of Chemical Engineering, Ryerson University, Toronto, Ontario, Canada M5B 2K3

Urea has the highest demand among all solid nitrogenous fertilisers within the agriculture industry. In this paper, a mathematical model and
an Artificial Neural Network (ANN) technique are proposed for the simulation and optimisation of the urea plant in an industrial petrochemical
company. The developed mathematical model consists of complex vapourliquid equilibria for the NH3 CO2 H2 O(NH2 )2 CO system in thermodynamic and reaction frameworks. The smart technique (e.g. ANN) considers the CO2 conversion in terms of temperature and the molar ratios of
NH3 /CO2 and H2 O/CO2 in the liquid phase. The ANN predictions were compared with the real data and results obtained from the mathematical
model. An acceptable agreement was attained between deterministic methods. Through implementation of a systematic sensitivity analysis, it
was found that a temperature of 191 C, a pressure of 132 atm and a NH3 /CO2 ratio of 2.7 are the optimum process conditions for the urea
production. It is concluded that the developed ANN (or connectionist) technique is an efficient tool for modelling complex phase equilibria with
reaction in the industrial urea plant.
Keywords: urea plant, simulation and optimisation, connectionist technique, ammonium carbamate, thermodynamics model

INTRODUCTION

itrogen-based fertilisers are the most broadly produced

kinds of fertilisers.[13] Among them, urea is the most
important product whose consumption is increasing significantly in the agriculture industry. In addition, urea is widely
used as a raw material in producing many chemical compounds
including plastics, chemical solutions, adhesives and medical
drugs.[24] Urea or carbamide is an organic compound with
the chemical formula (NH2 )2 CO. The German chemist, Friedrich
Wohler (1828), produced urea by reacting silver isocyanate with
ammonium chloride.[57] The synthesis of this organic material
from an inorganic compound made a great impact on the development of organic chemistry. The industrial production of urea
is based on the reaction of ammonia (NH3 ) and carbon dioxide
(CO2 ) at high pressure and temperature to form ammonium carbamate, which is consecutively dehydrated into urea and water.
Both the exothermic carbamate reaction and the endothermic urea
formation reaction often happen in the urea reactor of the industrial plants.[710] The reactor is designed such that its volume is big
enough for the desired urea production. In most of the technologies developed for urea synthesis, the main reaction takes place in
the liquid phase under pressure ranging from 13 to 25 MPa; while,
the reactor temperature is between 170 and 200 C.[6,7,10] Moreover,
the recent reactors are operated as adiabatic in practice.[1,7,10]
Transport phenomena (e.g. heat and mass transfer) between
existing phases and the kinetics of urea reaction govern the
behaviour of the urea reactor. Therefore, the conversion of carbamate into urea is not only controlled by the equilibrium
constraints of urea reaction as traditionally believed, but also by
the fluid dynamics contributing into the reactor operation.[710]
The widespread urea synthesis technologies were addressed
by several researchers.[1,3,10] These different technologies of urea

VOLUME 92, MARCH 2014

production mainly contrast on how urea is separated from the

raw materials and how NH3 and CO2 are recycled back to the
reactor.[5,11,12] The urea technologies include total or partial recycle of unconverted CO2 and NH3 in order to remove the restrictions
applied by chemical equilibrium on conversion of the raw materials to urea. Modifications of the production technologies are often
focused on enhancement of CO2 conversion, optimisation of heat
recovery and reduction in the utility consumption. Despite the fact
that modelling and simulation of the urea process is well treated
in the literature, there are still various key aspects to be explained
in the numerical modelling of such a complex process.[7,1315]
For instance, developing an accurate thermodynamics model is
necessary in order to predict the compositions of reactants and
products with high precision at different temperatures and pressures during the urea production process. Also, it is worthy to
propose a reliable tool (e.g. intelligent methods) for fast, low
cost and effective assessment of urea reactors in the absence of
adequate experimental or/and commercial data. Gorlovskii and
Kucheryavyi[16] developed an empirical equation after analysing
the urea conversion data reported by several authors.[1618] The
proposed correlation provides an accurate way to relate conversion of CO2 in the form of urea to H2 O/CO2 mole ratio which
is used in the current study.[1618] However, very few research
works have been published on biuret (NH2 CONHCONH2 ) formation, the major undesired by-product in the urea production

Author to whom correspondence may be addressed.

E-mail address: szendehb@uwaterloo.ca
Can. J. Chem. Eng. 92:469485, 2014
2013 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.21824
Published online 26 April 2013 in Wiley Online Library
(wileyonlinelibrary.com).

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469

process.[1618] Since biuret is toxic to plants, its content in fertilisers has to be kept as low as possible. Therefore, this by-product
should be considered in a comprehensive numerical modelling of
urea synthesis, as well. This will help controlling the operational
conditions of the urea reactor to lower the concentration of biuret
in the product stream.
The importance of urea production demands for energy conservation and environmental control mandates are the main
motivations to model and optimise the urea production reactor.
This paper addresses main aspects of an industrial urea plant
in terms of process engineering perspectives. The mathematical
modelling of the urea synthesis is complicated due to the formation of ammonium carbamate, an intermediate product and
the fluid dynamics. A mathematical model and an Artificial Neural Network (ANN) system are developed in this study based
on the thermodynamics and synthesis frameworks for the urea
reactor in the industrial plant of Shiraz Petrochemical Company
in South of Iran. This study utilises the MATLABTM and Aspen
Plus softwares for modelling simulation of the Stamicarbon CO2
process operating in the Petrochemical Company. A comprehensive Pressure/Volume/Temperature (PVT) study was carried out
using the Aspen Plus package in this paper. UNIQUAC model and
the modified PengRobinson (PR) equation of state (EOS) have
been used to calculate the equilibrium conditions of the liquid
and gas phases, respectively, for this rather complicated system.
Following the mathematical modelling and the sensitivity analysis, an ANN system was used to forecast the CO2 conversion and
thermodynamic behaviour in the chemical reactor. The CO2 conversion was considered as a function of temperature, NH3 /CO2
and H2 O/CO2 molar ratios. The optimisation of the urea reactor
was lastly performed using the ANN technique.
UREA PRODUCTION PROCESS VIA STAMICARBON METHOD
There are several commercialised processes proposed for urea production such as Stamicarbon process, Snamprogetti Process, Chao
process and Uchino process.[7,9,10] Stamicarbon method is one of
the most common processes for urea production designed and
commercialised by a Dutch company.[1,2,7] This type of process is
recognised as an acceptable and a fast growing process for producing urea.[1,7] In this production method, usually the generated
carbamate from ammonia and carbon dioxide enters the reactor
to produce urea in the form of a closed total recycle.
In general, the urea plant consists of three key parts: reactor,
stripper and condenser. First, carbamate is produced in the condenser and then it returns to the reactor through the gravitational
force. The tubular reactor is equipped with some trays for effective mixing of the phases. The inlet CO2 is injected with some
air to cover the wall of the reactor in order to prevent corrosion
in the system. Figure 1 shows the block diagram of the process
described.
The process used in the urea production plant of Shiraz Petrochemical Company is based on the Stamicarbon method. The
residence time in the reactor (about 28.5 m height and 2.5 m
diameter) is about 3040 min. In order to prevent the back mixing phenomenon and improve dispersion and contacting between
phases, the reactor is equipped with eight sieve trays. However,
these trays cannot eliminate the back mixing problem completely
and the reactor behaviour is far from an ideal Continuously Stirred
Tank Reactor (CSTR). On the other hand, the reactor cannot be
considered as a plug flow reactor, since the material streams
through the reactor are not in a plug flow movement. This is the
reason to model the reactor in the form of some CSTRs in series.

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THEORY OF UREA SYNTHESIS

Frejacques[8] proposed one of the early time kinetic models for the
chemical reaction of urea production; a reversible reaction for the
urea synthesis in the form[1,8] :
2NH3 (l) + CO2 (l) NH2 CONH2 (l) + H2 O(l)

(1)

This model was widely accepted among researchers up to

1952.[1] Thereafter, it was found by other researchers that the urea
production is a two-step reaction: synthesis of ammonium carbamate (NH4 COONH2 ), and then conversion of carbamate to water
and NH2 CONH2 .[7,12,19] Thus, the reactions are stated as:
2NH3 (l) + CO2 (l) NH4 COONH2 (l)

(2)

NH4 COONH2 (l) NH2 CONH2 (l) + H2 O(l)

(3)

Lemkowits[20] considered two conversion extents for the above

reactions and also determined Henrys constants for CO2 and NH3
in the reaction mixture based on experimental data. A number of
empirical correlations were proposed in the literature to calculate
the equilibrium mole fractions of the components in the reaction mixture system.[12,20] However, most of the studies have been
conducted within limited ranges of pressure and temperature.
MATHEMATICAL MODELLING OF UREA SYNTHESIS
REACTOR
Efficiency or performance of a chemical reactor depends mainly
on the rate of reactions, rates of mass and heat transfer and
intra-particle phenomena. Also, phase-equilibrium affects the
magnitudes of the components concentrations in the reactor.
During the last few decades, attempts were made to explain the
effects of non-ideality of the processes on reactor performance.
The mixing process is commonly evaluated considering two main
mechanisms: molecular mixing or micro-mixing, and bulk mixing
or macro-mixing.[21,22] This study focuses on the second approach.
The urea reactor is split into CSTRs in the proposed mathematical model. The modelling section includes thermodynamic and
chemical synthesis frameworks.
Although, there are some similar studies[10,12] in the literature which address the thermodynamic behaviour of the mixture
contributed in urea production process, the following main differences exist between the current research and previous studies
reported in the literature:
- Biuret production has not been considered in most of the previous studies; while, the current study includes the reaction rate
of biuret formation.
- The Equation of States (EOSs) selected in the previous studies
usually give the equilibrium data with some errors that arise
from inaccurate mixing rules and ignorance of cross association
between components present in urea production process. However, this paper addresses these shortcomings that lead to more
accurate thermodynamic results.
- Since there are always some uncertainties related to reaction
rates, EOS and non-ideality of the reactor, it would be valuable
if a robust tool such as ANN and fuzzy logics is tried to capture
all those uncertainties, even in the lump form, while predicting
process behaviour of a chemical engineering equipment in an
industrial plant. An efficient smart technique is employed here
and no such investigations on industrial urea reactors are found
in literature.

VOLUME 92, MARCH 2014

Figure 1. Block diagram of urea production process via Stamicarbon method.[2]

H2 O(g) H2 O(l)

Thermodynamics Basis
In general, the chemical reactions which are noticeable in the urea
synthesis conditions are as follows[7,12,23] :
CO2 (l) + 2NH3 (l) H2 NCOO + NH+
4

(4)

+
CO2 (l) + NH3 (l) + H2 O(l) HCO
3 + NH4

(5)

H2 NCOO + NH+
4 NH2 CONH2 (l) + H2 O(l)

(6)

2NH2 CONH2 (l) NH2 CONHCONH2 (l) + NH3 (l)

(7)

The chemical reactions involved in the urea synthesis occur in

the liquid phase. The liquid phase contains the components and

ions including, H2 O (1), NH3 (2), CO2 (3), NH+

4 (4), HCO3 (5),

H2 NCOO (6), H2 NCONH2 (7) and H2 NCONHCOH2 N (8).

The
volatility
of
urea
(H2 NCONH2 )
and
biuret
(H2 NCONHCOH2 N) is very low, and the ions are not able
to depart from liquid phase to vapour phase, thus only H2 O (1),
NH3 (2) and CO2 (3) are present in the vapour phase, meaning it
is necessary to consider vapourliquid equilibria (VLE) of these
three components with chemical reaction for this mathematical
modelling, simultaneously.
The VLE system is expressed with the following equations:
CO2 (g) CO2 (l)

(8)

NH3 (g) NH3 (l)

(9)

VOLUME 92, MARCH 2014

(10)

It is proved that the rates of reactions (4) and (5) are higher than
those of reactions (6) and (7).[6,7,10] Therefore, it is assumed here
that reactions (4) and (5) are at equilibrium conditions and equilibrium conversions can be considered for those reactions while
reactions (6) and (7) do not reach the equilibrium state. Thus,
particular rates for reactions (6) and (7) are required in order to
perform accurate numerical computations. The rate of reaction
(6), R, is expressed as follows[14,19,20,24] :


R = kCT x6


k = A exp

1 x7 x1
Kx,6 x4


(11)

E
;
RT

A = 2.5 108 s1 ;

E = 100 kJ mol1 (12)

where k is the reaction constant, Kx,6 is the equilibrium constant of

reaction (6) (refer to the Chemical Equilibrium of Urea Synthesis
System Section), E is the activation energy, xi is the mole fraction
of liquid component (i), and T and R are the temperature and
universal gases constant, respectively.
Formation of biuret is taken into account for this mathematical method. The reaction of biuret production is endothermic.
This slow chemical reaction occurs when the reaction mixture
contains a high concentration of urea and a small concentration
of ammonia at elevated temperatures.[2527] In the case of biuret

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471

formation, the equation of reaction rate suggested by Shen[27] is:

RBiuret = kCT2 (x7,0 x7 )2

(13)

where k is the reaction constant, and x7,0 is the initial mole fraction
of urea in the liquid phase. The parameters in Equation (13) are
presented as[27,28] :

E
k = A exp
;
RT

A = 2.1 10 m mol
7

ln f20 (T) =

1 1

s ;

E = 8.5 104 kJ mol1

(14)

In order to numerically perform any simulations of the urea

synthesis reactor, it is necessary to have a robust and adequate
thermodynamics model for the H2 OCO2 NH3 urea system. In
this study, the UNIQUAC model proposed by Sander[29] was used
to predict the activity coefficients of the components in the liquid
phase.
According to the phase equilibria, the fugacity of each component (fi ) in all phases is the same at equilibrium conditions as
shown in the following expression[21,22,30] :

fi = fi = = fi

(15)

where , and  illustrate the phases (e.g. gas, liquid and solid).
This study includes just gas and liquid phases.
Based on Equation (15), the following fugacity relationship can
be written for phase equilibrium of H2 O and NH3 components
(i = 1,2) in gas and liquid phases[21,22,30] :

vi P
xi i (T, x)fi0 (T, P = 0)exp
RT


= Pyi i (T, P, y)

v3 (P P1sat (T))
RT


= Py3 3 (T, P, y)
(17)

An expression for activity coefficient (ln  i ), which is valid for

non-polar substances, was suggested by Sander.[29]
The UNIQUAC model presents the activity coefficient in three
different terms[29,30] :
ln i (T, x) = ln iC (x) + ln iR (T, x) + ln iDH (T, x)
ln iC (x)and

(18)

ln iR (T, x)

are the combinatorial and residwhere

ual parts of the activity coefficient, respectively. These parameters

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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

A1
+ A2 ln T + A3 T + A4
T

(19)

In Equation (19), the units for f20 and T are MPa and K, respectively.
The constants of Ai in Equation (19) for calculation of the NH3
fugacity are as follows:
A1 = 2.5141 103 ;
3

A3 = 2.5759 10 ;

A2 = 0.28417;
A4 = 14.6460

The Henrys constant of CO2 in H2 O, H3,1 , is determined as

follows[21,22,30] :
ln H3,1 (T) =

2.6560 103
3.5050 101 ln T
T
+ 6.2316 103 T + 18.1575 + B3,1

(20)

where B3,1 represents the interaction between components H2 O

and CO2 . The expression for B3,1 is given by the following
equation[22,30] :


B3,1 = 18.1575 1.12 exp

2623.7
T


(21)

(16)

i (T, x) is the activity coefficient of component (i) that is a function of temperature (T) and liquid composition (xi ). fi0 is the pure
liquid reference fugacity of component i, depending on temperature. vi is the liquid molal volume of component i. i (T,P,y)
represents the fugacity coefficient of component i that is a function of temperature (T), pressure (P) and mole fractions of gaseous
components (yi ). It should be noted here that temperature and
pressure are in the ranges of 442456 K and 131.5133 atm along
the reactor height. Therefore, the above parameters are different
for various control volumes considered in the simulation runs as
the compositions of liquid and gas phases vary with height, as
well.
The phase equilibrium equation for CO2 (i = 3) is also written
as[21,22,30] :
x3 3 (T, x)H3,1 (T, P1sat )exp

depend on temperature and concentrations of the components in

liquid phase. ln iDH (T, x) is the DebyeHuckel contribution to the
activity coefficient which is defined differently for ionic and nonionic components. This part is a function of mole fractions of the
mixture components and temperature.
The temperature dependence of ammonias fugacity (f20 (T)) at
zero pressure is expressed by the following equation[21,22,30] :

Equations (15)(20) are used in the mathematical modelling to

calculate PVT data for the gas and liquid mixtures. These thermodynamic equilibrium relationships are solved with mass balance
and energy balance equations, simultaneously. It is important to
note that most of the parameters in these equations are functions
of compositions of the gas and liquid phases that are different
for each element and must be computed accordingly, considering
thermodynamics and chemical equilibrium at various temperatures and pressures. Further information about the parameters in
Equations (15)(20) can be found in Appendices A and B, and
these references.[2932]
It should be also noted here that PVT study of the mixture was
mostly conducted using the Aspen Plus software. The cross association effects due to polarpolar interactions between H2 O and
CO2 molecules which were not considered in the previous studies, is taken into account in the current work. The EOS used for
the gas phase in this study is cubic-plus-association (CPA) EOS
for water-containing systems that include combination of the PR
EOS and the thermodynamic perturbation theory for the physical
interactions and the hydrogen bonding of water molecules, respectively. Considering cross association between various molecules
and association between water molecules results in obtaining
physical properties of the mixture and the mole fractions of the
components with high accuracy. Technical reader is encouraged
to study Firoozabadi,[31] and Li and Firoozabadi[32] for more information.
CSTRs in Series Model
To simulate the reactor performance, it is necessary to derive
the corresponding mathematical equations. Since the reactor

VOLUME 92, MARCH 2014

9


l l
FJ,i
HJ,i +

3


i=1

FJ,i H J,i

9


i=1

l
l
Fj1,i
H j1,i

i=1

3


J
FJ1,i H J1,i = Q

i=1

(24)

Figure 2. Schematic of the element considered for reactor simulation.

behaviour is non-ideal, the kinetic model proposed here is based

on n number of CSTRs in series. In this model, the cylindrical
reactor is divided into n tanks and the material and energy balance equations are written for each tank as a volumetric element
(see Figure 2). Finally, the conversion distribution and also temperature profile are determined through solving the governing
equations of n-CSTRs, simultaneously.
Subscript J denotes the element number and superscripts l and
g denote liquid phase and gas phase, respectively. Using the material balance for the element J, the mass conservation equation is
written as follows:

FJ,i FJ1,i = V

7


ri RrJ

J = 1, 2, 3, . . . , n

(22)

J would be
The reactor is operating adiabatically, therefore Q
equal to zero.
g
l
In Equation (24), H J,i
and H J,i are partial enthalpies of component i in the element J for the liquid and gas phases, respectively.
xi also denotes the mole fraction of component i.
In the urea reactor, there are liquid and gas phases such that
they contact with each other along the reactor height and then are
mixed on the reactor trays. As seen in the equations of mass and
energy balances, there are several terms including the properties
of the components in each phase to compute the reactor efficiency
and concentration distribution. In addition, the rates of chemical
reactions (e.g. Equations 11 and 13) include mole fractions of the
components in liquid phase as well as equilibrium constants of
the reactions in the mixture. Therefore, an appropriate thermodynamics model for the system (H2 OCO2 NH3 urea) was selected
to determine the values of the terms explained above. More information about thermodynamic and synthesis frameworks are given
in Appendices A and B.
Chemical Equilibrium of Urea Synthesis System
As explained earlier, reactions (4) and (5) play the most important role in the chemical equilibrium of the components at the
conditions that the urea synthesis takes place:
The equilibrium constant as a function of temperature is
obtained for the above two reactions as follows[21,22,25] :
ln Kr (T) =

C1,r
+ C2,r ln T + C3,r T + C4,r
T

(25)

The coefficients values of Equation (25) for the chemical reactions are presented in Table 1.
The equilibrium constant is defined as shown below[21,22,30] :
Kr (T) = Kx,r (x)K,r (T, x)

r=4

FJ,i is the molar flow rate of the component i in both liquid and
gas phases in the element J. V is the volume of each element
(the total volume of the reactor is about 140 m3 , thus the volume
of each element is calculated by dividing the reactor volume to
the number of the elements), ri is the stoichiometric coefficient
of component i in reaction r, RrJ is the reaction rate and n is the
total number of elements or CSTRs. Although, the urea production
reaction takes place in the liquid phase, the total volume of the
reactor (V) should be taken into account in Equation (22), since
the reaction rates of urea and biuret (e.g. Equations 11 and 13)
are expressed in terms of CT which is the total concentration of
the components in the mixture. On the other hand, Equation (22)
includes molar flow rates of both liquid and gaseous components
in the reactor. Hence, considering only liquid volume in the mass
balance equation gives wrong results while modelling the urea
synthesis process.
The energy balance of the reactor can be written as follows:

(26)

For instance, Kx,r (x) and K,r () for Equation (5) or r = 5 are
presented in the forms of the following expressions:
Kx,5 =

x4 x5
x1 x2 x3

(27)

K,5 =

4 5
1 2 3

(28)

For reaction (4), the similar relationships are written for Kx,r
and K,r .
The required equations to predict the reactor behaviour are
three thermodynamic equilibrium equations for three components (NH3 , CO2 and H2 O), eight molar balance equations for

Table 1. The values of coefficients in Equation (25)

Parameters

[Rate of Energy Input] = [Rate of Energy at Outlet]

Function (ln Kr )

+ [Rate of Energy Consumption]

[Rate of Energy Generation]

VOLUME 92, MARCH 2014

(23)

r=4
r=5

103 C1,r

102 C2,r

103 C3,r

C4,r

9.9068
8.8226

7.4296
0.8404

5.3985
1.8736

20.222
21.6135

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473

all eight components involved in the urea synthesis process, and

one energy balance equation. The unknown parameters are molar
flow of all components (eight variables) in the liquid phase, molar
flow of gaseous components (three variables) including NH3 , CO2
and H2 O and temperature of the output system (one variable). All
equations of the reaction rate and chemical equilibrium in the
form of supplementary equations are included in the mole balance relationships of the components. The input data are also
molar flow of the input chemicals, reactor volume, temperature
and pressure. It should be also noted that the pressure is kept
constant during the process.
The governing equations to obtain unknown variables are as
follows:
(1) Three equations for the phase equilibrium of H2 O (1), NH3
g
(2), CO2 (3): fi = fil ; i = 1, 2, 3.
(2) Eight equations for the material balance:

FJ,i FJ1,i = V

7


ri RrJ

r=4

J = 1, 2, 3, . . . , n

and

i = 1, 2, . . . , 8
Figure 3. A simple structure of an ANN with one hidden layer.

As mentioned earlier, there are seven reactions (Equations

410) in the urea system; however, three of them (Equations 810) just show thermodynamic equilibrium for CO2 ,
NH3 and H2 O, respectively. In fact, four main reactions in
the urea process include formation of ammonium carbamate
(e.g. Equation 4), reaction between all three main components (e.g. Equation 5), formation of urea (e.g. Equation 6)
and formation of biuret (e.g. Equation 7).
(3) One equation for the energy conservation: Equation (25) or
(24).
(4) Two supplementary equations for chemical equilibrium of
reactions (4) and (5).
In order to calculate the unknown parameters explained above,
the numerical modelling was performed using the MATLABTM and
Aspen Plus software packages in this study. It is important to note
that all thermodynamic and physical properties of the individual
components and the mixture were computed for each certain set of
T, P, and compositions using the Aspen Plus software and then the
data obtained at this stage were exported into a MATLAB program
that was written to perform modelling of the urea reactor through
a synthesis framework. The framework defined in the program is
based on the analogy of CSTRs in series that is combined with
thermodynamic section at each simulation run.
ARTIFICIAL NEURAL NETWORK
ANN is a robust technique which is able to capture and represent complex relationships between inputs and outputs. ANN
has been developed from the information processing mechanisms
of the brain.[3336] The theory of ANN was developed initially
by McCulloch and Pitts.[36] Over the last few years, ANN has
been broadly employed for numerous applications such as process control, behaviour prediction, model recognition and system
classification. An ANN model is composed of a large number of
interconnected neurons which can be considered as a computing engine that receives inputs, processes them in a hidden layer
and then generates an output. The main advantage of ANN systems in contrast with conventional methodologies is that they
do not need the intricate nature of the process under study. The

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key shortcoming of ANNs is that they normally act as a blackbox, not capturing important aspects related to the physics of the
modelled phenomenon or process. However, a systematic mathematical model is proposed in the present study to support the
results of the ANN model and also describe the complex dynamics of urea reactor in a proper manner. Figure 3 depicts a simple
architecture of an ANN with one hidden layer. The numbers of
neurons and hidden layers depend on the complexity and nonlinearity of the problem. Each neuron is connected to the input and
output by a corresponding weight. Inputs to each neuron are multiplied by their corresponding weights. After that, the products are
summed up, and the sum is processed using a nonlinear transfer
function to obtain an output.[3335] Initial values of weights are
randomly assigned by employing uniform or Gaussian distribution. The weights are modified through a training process until
the error between the actual output and the predicted output is
minimised. There are number of different neural network structures, and learning algorithms (e.g. back propagation (BP) and
multiple layer perceptron (MLP)) for the ANN technique.[3335]
The BP method is recognised as one of the most general learning
algorithms that modify the weights from the output layer back
to the input layer at each iteration until the mean squared error
(MSE) meets the tolerance specified for the problem.[3336] The BP
algorithm adjusts the weights using the gradient descent principle
where the change in the weight is proportional to the error gradient with a negative sign.[3335] The performance of the ANN model
is finally checked by introducing new and independent datasets
to the trained model. Additional details on the ANN technique can
be found in these references.[3336]
Five important stages are usually required to design an ANN
model. These steps described in brief are as follows:
(1) Data collection: The first stage is collecting and preparing
data. As noted in this study, the experimental and real data for
temperature, NH3 /CO2 , H2 O/CO2 , and conversion percentage
are collected from the literature.
(2) Data preprocessing: After the required data are collected, normalising and randomising the data are necessary to attain

VOLUME 92, MARCH 2014

reasonable and unbiased results. Data normalisation should

be done due to large differences between magnitudes and
units of various variables contributing in the ANN model.
(3) Network construction: The designer should determine the
number of hidden layers, the number of neurons in each
layer, transfer function in each layer, training function, weight
learning function and performance function at this stage.
(4) Training phase: The weights are adjusted at this stage as an
acceptable match is obtained between the real data and predicted outputs.
(5) Testing phase: Examining the performance of the developed
ANN model is the last. Unseen data (the data that have not
been employed in the training stage) are considered for the
testing stage. Statistical parameters such as the coefficient of
determination (R2 ), and the MSE are calculated using the
ANN predictions in order to assess the performance of the
ANN system quantitatively and make sure whether there is
any particular trend in the performance of the ANN model.
OPTIMISATION METHOD
Our purpose in the optimisation phase of this study is to obtain a
series of optimum input parameters to minimise a certain performance indicator. However, there are generally a number of
uncontrollable and unmeasurable factors in a real process to make
it complicated to achieve our goal. It is assumed that the mean
of these disturbances approaches to zero. Also, the average value
of a certain input variable in a long duration is considered as the
real steady input for a given parameter. Based on the assumptions
taken, the performance index is related to the mean values of the
input parameters. Then, a set of optimal averages of the input
variables is searched to solve the optimisation problem.
The optimum stochastic objective function (I ) is given by:
I = f (F[u(t)], w(t), v(t), t)

(29)

where w(t) and v(t) are the random disturbances of process whose
average are zero. u(t) is the random input variable. F[u(t)] is the
mean value of u(t) at steady state condition. For the sake of simplicity, the objective function, I(t), is considered as the output of
the ANN network, y(t).
I(t) = y(t)

(30)

To minimise the average value of the stochastic objective function (I(t)), the solution of the optimal problem can be obtained
through the following relationships:
F[I(t)]
= 0 at F [u(t)]
F[u(t)]

(31)

The mean values of the input parameters are updated as below:

F[u(t)] = 

F[I(t)]
F[u(t)]

(32)

Here,  is a positive step size.

The optimum values of the system input variables are taken
into account as the optimal set points for the important variables
in the controllers of a given process. It should be noted here that
the steepest descent method is employed to do the optimisation
computations. The optimisation framework using ANN is depicted
in Figure 4.

VOLUME 92, MARCH 2014

Figure 4. A schematic of optimisation procedure via ANN.

Stochastic process referred in this study considers measuring or

collecting the input and output variables (they may have uncertainties) contributing in the urea production. It is recommended
that the important parameters are identified based on the physics
and mathematical modelling of the urea process. These data are
usually collected from the literature and/or real plants and then
employed in the smart or predictive tools such as ANN system.
In fact, the grey-box model introduced in this study for the urea
production is a comprehensive study with logical formulations
in terms of mass conservation, energy conservation and thermodynamic behaviour. However, the main concerns regarding the
model include uncertainties with reaction rates, mixing rules of
the EOS and non-ideality of reactor. The ANN model is examined
to lower the effect of the uncertainties on the predicted results.
On the other hand, running the simulation program with complicated nonlinear equations is generally time-consuming and costly.
To overcome this problem, the smart method is used in this study.
The ANN model is able to optimise the urea production and also
predict the behaviour of urea reactor with different scales. It also
assists engineers to scale-up and/or improve the process through
a quick and reliable manner.
RESULTS AND DISCUSSION
As highly exothermic reaction of carbamate formation takes place
mainly at the interface among the liquid and gas phases, heat and
mass transfer from the interface to the bulk of the phases appears
to be an important feature while modelling the process behaviour
of the urea synthesis reactor. In addition, the fluid dynamic (e.g.
size of bubbles and rise rate) may play an important role in the
reactor performance. However, considering these aspects requires
detailed operational data (e.g. pressure variation and concentration profile) and more information about the internal parts (e.g.
tray). Providing all required data is a time-consuming and fairly
costly task. This is the main reason that ANN is applied in this
study to take into account all uncertainties through employing
adaptive parameters in the network.
In order to validate the mathematical and ANN models developed for urea synthesis reactor, the results predicted by the models
are compared to the actual data of the urea synthesis reactor in Shiraz Petrochemical Company. It should be noted here that typical
industrial operating conditions (real data) of the urea plant have
been collected from the process control room by the first author of
this paper. Furthermore, the introduced models are employed to
investigate the effects of temperature, and flow rates of H2 O, NH3
and CO2 on the conversion percentage. At last, the optimisation
process is carried out to obtain the optimal conditions that lead
to a higher conversion in the urea reactor.
Results of this study show that the proposed modelling methodology is a practical approach in analysing the plant performance

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

475

Table 2. Predicted results and industrial data for molar flow rates in
the liquid phase
Flow rate (kmol/day)
Components in liquid phase

Predicted

Actual

NH3 (input)
NH3 (output)
CO2 (input)
CO2 (output)
H2 O (input)
H2 O (output)
Urea (input)
Urea (output)

116 180
79 580
38 330
18 410
18 700
45 660
170
25 490

117 356
80 082
41 334
20 163
18 383
45 344
208
26 609

and improving plant operation such as energy saving, high

conversion and identification of bottlenecks. Furthermore, the
methodology is a solid base for further optimisation efforts and
developing on-line control systems for the urea reactor.
Mathematical Method
In this study, the simulation part conducted by employing the
Aspen Plus and MATLAB softwares covers the condenser, stripper
and reactor parts, since the governing mass and energy equations
are similar for these three important elements (governing equations for the condenser and stripper are given in Appendix C).
Starting mathematical modelling from the condenser, chemical
and thermodynamic equilibrium relationships are applied to this
part when temperature and molar ratios of NH3 /CO2 and H2 O/CO2
are the known variables for this phase of simulation. The real
data and the results obtained from the mathematical approach are
shown in Tables 2 and 3 for both liquid and gas phases involved
in the urea reactor of the commercial plant. A good agreement
is observed between the model outcomes and the actual process
data.
The results of this numerical computation in more details are
illustrated in Figures 510. The amount of the produced urea in
the reactor versus the input H2 O moles is presented in Figure 5.
As shown in the figure, the amount of produced urea will decrease
when the flow rate of the water introduced into the reactor
increases. This is because the water phase acts as a by-product in
the system of the urea synthesis reaction. Therefore, it improves
the reaction (see Equation 6) in the reverse direction of urea

Figure 5. Effect of flow rate of water introduced into the reactor on the
amount of urea produced.

production according to the Le Chateliers principle, while the

amount of produced water increases.
Figure 6 shows the temperature distribution along the height
of reactor. An increasing trend for temperature is predicted versus the height of reactor. This behaviour is acceptable since the
urea production reaction (combination of reactions (4) and (6))
is generally exothermic.
The flow rates of the components of the reaction mixture for
various points within the reactor are shown in Figure 7. As seen
in the figure, the flow rates of NH3 and CO2 will decline versus the
length of the reactor as the temperature increases. This increase in
temperature enhances the urea reaction and consequently causes
high consumption of NH3 and CO2 in the process system. Following the same logic, reverse patterns for H2 O and urea components
(as main products) are observed in Figure 7.
As expected, the amounts of the products increase from the
bottom to top of the reactor, while a reduction in the flow rates of
the reactants contributing in the production of urea is observed.
Also, there is a good agreement between the simulation results
and the commercial reactor data, as depicted in Figure 7.

Table 3. Modelling results and industrial data for flow rates in the gas
phase
Flow rate (kmol/day)
Components in gas phase
NH3 (input)
NH3 (output)
CO2 (input)
CO2 (output)
H2 O (input)
H2 O (output)
N2 (input)
N2 (output)
O2 (input)
O2 (output)

476

Predicted

Actual

32 129
15 422
10 440
4620
1660
750
1387
1387
213
213

32 381
13 433
10 794
4249
1687
726
1387
1387
213
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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

Figure 6. Temperature profile in the urea reactor according to the

simulation results and the commercial plant data.

VOLUME 92, MARCH 2014

Figure 9. Effect of the feed temperature on the reactor height while

having the same conversion for all heights.
Figure 7. Flow rates of the mixture components over height of the
reactor based on the modelling outputs and the real data.

According to the synthesis model chosen for this study, the real
reactor is divided into n-CSTRs (or backmix reactors) in series
in a way that the total volume of them is equal to that of the
real reactor. First, low number (e.g. one or two) of CSTRs in
series is selected to simulate the non-ideality behaviour of the real
reactor. Then, the material and energy balance equations are written for each tank as a volumetric element. Finally, the conversion
distribution and also temperature profile are determined through
solving the governing equations of n-CSTRs, simultaneously. If
the temperature and CO2 conversion (the amount of urea produced) from the modelling part are very close to the real data,
then the first guess about the number of CSTRs is correct; otherwise, the number of the backmix reactors is changed and the
same computation will be carried out. This procedure will proceed until a good agreement between the modelling outputs and
the actual data is observed.
Figure 8 shows the effects of the number of CSTRs on the predicted conversion of CO2 to urea for the output stream of the urea
reactor at the real operating conditions. As shown in Figure 8,
the performance of the reactor increases as the number of CSTRs

Figure 8. Reaction conversion versus number of CSTRs.

VOLUME 92, MARCH 2014

increases. However, there is a characteristic number of CSTRs at

about n = 12 after which no significant change was experienced
in the magnitude of conversion. Therefore, 12 CSTRs can simulate
chemical reaction and thermodynamic behaviour of this non-ideal
reactor of urea production. Moreover, the results illustrated in
Figure 8 convey this massage that the eight sieve trays placed
in the reactor are not able to maintain complete mixing. It should
be noted here that the number of stages would be equal to the
number of trays in the case of perfect mixing.
In fact, only real temperature and CO2 conversion at the reactor
outlet are required to calculate the number of CSTRs while modelling the non-ideality of the urea reactor. However, more real
data including temperature and CO2 conversion of the inlet and
middle points of the reactor are added to Figure 8 in order to
have a better comparison between the real data and theoretical
results. The method proposed by Stamicarbon Staff[2] for measuring the compositions is to install N/C measurement devices on
various locations (e.g. inlet, middle part and outlet) of the reactor. In this technique, the samples taken from the urea reactor first
pass through a sampling process (e.g. cooling, pressure reducing
and flushing). Then, they are analysed by the density meter, GC
and HPLC to determine the mixture compositions and N/C ratio.
All these sampling and measuring parts are placed in a cabinet,
known as N/C measurement system.

Figure 10. Conversion of CO2 to biuret versus temperature of reactor

feed.

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477

As mentioned earlier, the number of trays employed in the real

reactor is 8 considering that an efficiency of 6575% for each tray
was reported by Stamicarbon Staff[2] and Dente et al.[6] The gas
and liquid passing through the reactor mix with each other and
uniform concentrations and temperature are attained on each tray.
Thus, it is reasonable to simulate the actual reactor in the form
of 12 CSTRs based on the tray efficiency. Also, the modelling
simulation conducted in this study shows that the output temperature will not be suitably matched with the real temperature
of the reactor outlet if greater numbers of CSTRs are considered for simulation of the real urea reactor. On the other hand,
a number of CSTRs higher than 12 moves towards the plug flow
restraining behaviour within the error of control instruments and
also sampling and laboratory methods. In addition, an acceptable
agreement between the real data and the results obtained from the
synthesis and thermodynamic implies that 12 CSTRs can approximate the reactor behaviour in terms of concentration back-mixing
and residence time distribution (RTD).
Based on the numerical investigation conducted here, if the feed
with the higher temperature is provided for the synthesis reactor, it
would be possible to lower or prevent producing biuret in the exit
stream. In this case, if the temperature of the production stream
is controlled well, the same conversion can be attained using a
shorter reactor (see Figure 9). A trade-off between energy cost
for heating and the manufacturing cost for the reactor is very
important to make an economical decision in this situation.
As noted before, the urea synthesis becomes more complicated
by the production of biuret that should be kept at a low level,
since it unfavourably influences the growth of various plants.
The current modelling simulation addresses the effects of various parameters such as feed temperature and reactor length on
the amount of biuret produced in the urea plant. The effect of
feed temperature on the conversion of CO2 to biuret is illustrated
in Figure 10. Although, an increase in temperature increases the
CO2 conversion to urea, it may cause producing a by-product
called biuret. Figure 10 clearly depicts that as the temperature
increases beyond 440 K; the favourable conditions for advancing the reaction of biuret formation would be achieved, leading
to production of higher amount of biuret in the product stream.
Thus, controlling condenser and reactor pressures, which affect
the temperature of the feed and product streams considerably,
is inevitable in the urea synthesis loop through setting a proper
process engineering strategy. The distribution of biuret produced
along the height of the urea reactor is demonstrated in Figure 11.
This figure was obtained based on the operating conditions (e.g.
P = 131.5 atm) of the real urea reactor. The conversion of CO2 to
biuret is increased as the reaction mixture goes up along the reactor height and obtains higher temperatures. Again, it is confirmed
that a strong dependency exists between the pressure, temperature and the reactor height. Therefore, it is necessary to find the
optimal conditions as the conversion percentages of CO2 to urea
and biuret have the maximum and minimum values, respectively.
According to both Figures 10 and 11, a reasonable match is noticed
between the simulation results and the real data, indicating the
appropriateness of the mathematical modelling employed in this
study. It is important to note that N/C measurement devices are
installed on the reactor to obtain the biuret flow rate.
The mathematical model sensitivity to variations in NH3 /CO2
and H2 O/CO2 ratios in the urea synthesis unit is presented here. In
Figure 12, the equilibrium conversions predicted by this numerical modelling are compared with the experimental data reported
by Gorlovskii and Kucheryavyi.[16] As seen in Figure 12, it can be
concluded that the proposed thermodynamics model could predict

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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

Figure 11. Variation of biuret production rate in the commercial plant

with reactor height.

the phase behaviour of the mixture contributing in the urea synthesis in the industrial plant, considering the average relative error
for equilibrium conversion is about 6.7%. Therefore, the present
study clearly provides an accurate fit of the real/experimental data
published in open sources.[1618]
ANN Method
Based on the phase rule, the degrees of freedom (F) for the urea
system are determined by:
F =C+2

(33)

where C is the number of independent components and  is the

number of phases.
In our case, the number of phases is two and the independent
components are three, including ammonia (NH3 ), carbon dioxide
(CO2 ) and water (H2 O) in the liquid phase. Therefore, F = 3 for the
system under study. According to the literature, these three independent parameters are usually temperature, and the molar ratios
of NH3 /CO2 and H2 O/CO2 .[7,9,10] Thus, the ANN model considered

Figure 12. Conversion percent of CO2 to urea at 445 K under

equilibrium conditions. A comparison between the modelling outputs
and the experimental data of Gorlovskii and Kucheryavyi.[16]

VOLUME 92, MARCH 2014

these three independent variables as input parameters. Input data

was normalised before starting the ANN modelling to avoid any
false influence of factors with higher order of magnitude. Data
normalisation was performed using Equation (34) as follows:
X=

x ((xmax + xmin )/2)

((xmax xmin )/2)

(34)

where xmax and xmin are the highest and lowest values of variable x, respectively. The ANN model was trained using 125
experimental and/or commercial plant data taken from these
references.[1,6,7,10] The training dataset was selected randomly
from the available urea synthesis data (85% of the whole data),
covering a temperature range of 435485 K, NH3 /CO2 range of
2.06.5 and H2 O/CO2 range of 0.11.4. The back-propagation
method was used to modify the weights until the MSE became
less than 0.005. MATLAB software version 7 from Mathworks,
Natick, Massachusetts was employed for the ANN modelling. The
LevenbergMarquardt optimisation algorithm was the BP technique selected for training the neural network. The algorithm is
the fastest BP algorithm in MATLAB toolbox. Hyperbolic tangent
sigmoid and linear functions were the transfer functions for the
hidden and the output layers, respectively. The performance of
the ANN model was tested by 17 new and independent datasets.
Any ANN model contains one input layer, one output layer and
one or more hidden layers. According to the universal approximation theory, one hidden layer with a sufficient number of neurons
can model any set of input/output data to a reasonable degree
of accuracy.[37] Thus, one hidden layer was selected in the ANN
model developed in this study. Table 4 shows the performance of
neural network models with various numbers of neurons in a single hidden layer. The performance of the network was tested by
calculating the coefficient of determination (R2 ), mean absolute
percent error and maximum/minimum absolute percent errors
for both training and testing datasets. It should be noted here
that R2 is a statistic parameter which gives information on goodness of fit in a model. In regression analysis or fitting of a model,
the R2 coefficient is a statistical measure of how well the model
line approximates the real data points. An R2 of 1.0 indicates the
model line perfectly fits the data. The following equation shows
the mathematical definition of R2[38,39] :
n


R =
2

i=
n

(yiP y M )2
(35)
(yiM y M )2

i=1

where yM and yP represent the measured and predicted output parameter (e.g. CO2 conversion percentage), respectively. y M
stands for the average of the measured yi data.
R2 was found higher than 0.998 for neural networks with 4
and higher numbers of hidden neurons. High values for mean
and maximum percent errors were obtained when the number of
neuron was less than 4. Increasing the number of neurons from 2
to 8 lowered the mean percent error by 93% from 66.4% to 4.5%.
The maximum and minimum absolute errors for the network with
eight neurons were 17% and 0.01%, respectively. Increasing the
number of neurons from 8 to 10 increased the maximum absolute percent error of the training and testing phases by 31% and
44%, respectively. Thus, the optimum ANN model was found to
have one input layer with three neurons, one hidden layer with
eight neurons and one output layer with one neuron (refer to
Table 4). Higher numbers of hidden neurons were avoided in order
to prevent overtraining of the ANN model. This important point
should be considered while performing the training phase in ANN
systems.[3336]
As seen in Figures 13 and 14, a comparison between predicted
and measured CO2 conversion to urea at training and testing
phases for the ANN model was conducted in this study. It is clear
from Figures 13 and 14, the outputs of the model simulated with
ANN exhibit an acceptable agreement with the actual data of the
urea reactor and also the experimental data available in the literature. The references for the data used in the ANN model include
the following studies and/or documents.[1,6,7,10]
Optimisation Study
It is assumed that the input and output variables are random
parameters for the process under study. The urea reactor includes
a feed stream that has a gaseous phase and a liquid phase containing ammonia and carbon dioxide. The mole ratio of NH3 to CO2 in
the feed is A(t). The temperature of the feed is established by the
pressure of the boiler stream Pf (t) in the ammonium carbamate
condenser. This plant has liquid and gas outputs at the bottom and
top of the reactor, respectively. It is a reasonable assumption that
the load of the plant remains constant.[13] However, the values
of Pf (t) and A(t) regularly change with noise.
Regardless of economical considerations, an optimal operating
condition is usually determined to maximise the conversion of
CO2 . It is known in the commercial urea plant that the system
pressure has the lowest value when the operating load is not
changed.[1,2,4] In this case, the conversion of CO2 to urea is at its
highest level. Thus, the minimum system pressure, P(t), is chosen as the objective function. There are two main manipulating

Table 4. Performance of ANN with various numbers of neurons in one hidden layer
Training dataset

Neuron no.
2
3
4
5
6
7
8
9
10

Testing dataset

R2

Max. abs.
% error

Min. abs.
% error

Mean abs.
% error

R2

Max. abs.
% error

Min. abs.
% error

Mean abs.
% error

0.995
0.995
0.999
0.998
0.998
0.999
0.999
0.999
0.999

1475
1358
341
603
372
291
17
31
44

0.40
0.13
0.00
0.01
0.27
0.00
0.01
0.00
0.00

66.4
90.8
33.7
27.8
33.5
21.3
4.5
5.7
5.0

0.997
0.996
0.997
0.999
0.997
0.996
0.998
0.994
0.995

275
425
171
150
127
177
15
56
45

0.99
1.21
0.34
0.65
0.43
3.94
0.17
13.41
0.35

67.1
86.6
34.8
46.3
34.0
30.4
9.4
14.0
10.4

VOLUME 92, MARCH 2014

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

479

Figure 14. Performance of the developed ANN model based on R2 : (a)

training phase, and (b) testing phase.

Figure 13. Measured versus predicted CO2 conversion using the ANN
model: (a) training, and (b) testing.
Figure 15. Optimisation network for urea reactor.

variables to the system pressure, namely, proportion of ammonia

and carbon dioxide in feed, A(t), and the boiler stream pressure,
Pf (t).
Having A(t) and Pf (t) as the input variables, and P(t) as the
output variable, a BP neural network was employed. The network
comprises one input layer (two input neurons), one hidden layer
(three hidden neurons) and one output layer (one output neuron)
as shown in Figure 15.
From the urea plant in Shiraz Petrochemical Company, several
sample patterns in terms of steam pressure (Pf ), NH3 /CO2 (A) and
system pressure (P) were collected every 30 min. The process data
are given in Table 5 for sample number (k) = 1, 2, . . . , 60.
The initial weights equal to one are selected in the neural network. Also, the learning step is set on 0.05. The error function is
given as follows:
1
2
e=
(P(kT) P(k))
2
60

(36)

k=1

are the sample output and the network

where P(kT) and P(k)
output, respectively. It was found that about 440 iterations are

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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

required to attain the error value close to zero. Then, 15 average value patterns ((F[A(t)], F[Pf (t)]), F[P(t)]) are considered to
train this network. After 55 iterations, the error function satisfies the desire condition. Once the training phase is completed,
some of new sample patterns are picked to examine the generalisation potential of the learned network. This part gives acceptable
results. To do the optimisation task, the steepest descent method
is used to solve the problem. The conditions for optimisation are

Table 5. The process data for the urea synthesis reactor

Sample no., k

A (kT)

Pf (kT), bar

P(kT), bar

1
2
3
4
..
.
60

2.45
2.53
2.49
2.56
..
.
2.57

10.36
10.41
10.34
10.44
..
.
10.38

130.52
130.47
130.54
130.45
..
.
130.51

VOLUME 92, MARCH 2014

as below:
F[P(t)]
= 0 at F [A(t)], F [Pf (t)]
F[A(t)]

(37)

F[P(t)]
= 0 at F [A(t)], F [Pf (t)]
F[Pf (t)]

(38)

The optimum outputs are as follows:

F [A(t)] = 2.54
F [Pf (t)] = 10.37 bar
F [P(t)] = 130.49 bar
Also, optimal conditions using the mathematical model were
determined through a trial and error procedure where the CO2
conversion to urea is maximised without economical considerations. According to this phase of study, NH3 /CO2 molar ratio of
2.7, the condenser feed pressure of 10.5 bar and system pressure
(P) of 132 bar are the optimal values for the process parameters.
Using the equations for thermodynamic equilibrium (Equation
15) and energy balance (Equation 23 or 24), the temperature corresponding to this optimum pressure was determined equal to
191 C which is the temperature of the output stream of the reactor. The amount of biuret produced at the optimum conditions
is predicted to be about 75 kmol/day which is much lower than
the biuret flow rate (e.g. 170 kmol/day) in the urea reactor of Shiraz petrochemical company at current operational conditions. As
the optimum temperature of exit flow for real cases is usually in
the range of 184195 C, the optimum temperature found in this
study would be within the tolerable upper limit of the temperature range and the amount of urea produced in the plant. The
acceptable closeness between optimisation data from mathematical modelling and ANN systems shows clearly the validity of the
optimisation part of this study. It seems reasonable that the mean
values of NH3 /CO2 , Pf and P obtained from these two different
independent methods can be considered as operating conditions
to determine maximum amount of urea produced in the reactor.
The optimum pressure is neither the lowest nor highest pressure. As the reactor pressure increases, its temperature goes up. To
investigate the effect of pressure (or temperature) on the amount
of urea produced, both reactions including carbamate formation
and urea formation should be considered. As production of ammonium carbamate is exothermic, increasing the temperature lowers
the amount of ammonium carbamate formed in the process.
Endothermic reaction of urea formation will gives higher amount
of the product when the temperature is increased. Therefore, there
is an optimum value for the pressure (temperature) because of
the opposite influences of pressure on these two reactions taking place in the reactor. On the other hand, further increasing
temperature or pressure causes production of biuret which is an
undesired product in the urea production process. Such a physical justification confirms the correctness of the optimum pressure
obtained in this study, again.
It is clear that if the ratio of NH3 /CO2 and the amount of urea
produced in the reactor are kept constant, it would be easier in
terms of process control to operate the reactor at the lowest pressure that provides more suitable environment for production of
ammonium carbamate. It also saves more energy during the plant
operation.
It is worth noting that the carbamate condenser in the Stamicarbon technology is actually a heat exchanger in which the heat

VOLUME 92, MARCH 2014

generated during condensation of ammonia and carbon dioxide to

form ammonium carbamate in the tube side is used to produce low
pressure (e.g. 1020 bar) steam in the shell side being employed
in other parts like stripper. Generating the steam with low pressure is based on a systematic engineering design planned by the
Stamicarbon Company through Pinch technique for minimising
energy consumption in the urea plant.
From the optimisation study and also the parametric sensitivity analysis conducted using the numerical modelling program,
it was found that increasing pressure of the condenser causes an
increase in the temperature, leading to more formation of ammonium carbamate in the stream exiting from the condenser (the
plant unit prior to urea reactor) that provides a better condition
for urea production. Therefore, higher conversion percentages can
be achieved at any specific elevations of the urea reactor if the condenser works at higher pressure. Also, the same amount of urea
can be produced in a reactor with smaller volume under higher
operating pressure condition.
ANN and Mathematical Models Versus Real Case
Predictions obtained from neural network model and mathematical systems were compared against the real data of urea reactor in
Shiraz Petrochemical Company. Table 6 gives the correlation coefficient (R2 ), MSE, maximum absolute percentage error (MAPE)
and minimum absolute percentage error (MIPE) for the ANN and
mathematical models to predict the amount of urea production.
The statistical information clearly demonstrates that both ANN
and mathematical models work properly to predict thermodynamic and synthesis behaviours with high precision. The higher
value of R2 for ANN compared with the mathematical modelling in
this study indicates a very satisfactory performance for the developed neural network model. The proposed ANN model enhanced
the results from the thermodynamic and synthesis frameworks
and the MSE and MAPE were decreased to 64.3% and 53.1%,
respectively. Improvement in estimation of CO2 conversion with
respect to R2 was approximately 5.4%. The obtained results also
indicate that the ANN model proposed here is a proper tool for fast,
inexpensive and reliable prediction of amount of urea produced
in synthesis reactor in the absence of sufficient experimental and
commercial plant data.
As Table 6 and Figure 13 show, there is a reasonable agreement
between the computer simulations and ANN model results with
the commercial plant data.
The Relative Effects of Input Variables
A sensitivity analysis was conducted for the developed ANN
model using the analysis of variance (ANOVA) technique.[38,39]
Dependence of the output variables (CO2 conversion) on each
of the independent variables was also examined. The results
obtained from the sensitivity analysis are presented in Figure 16.
A higher correlation between any input variable and the output variable indicates greater significance of the variable on

Table 6. Performance of the proposed ANN and mathematical

models to predict the behaviour of urea reactor
Parameter

Mathematical model

ANN model

R2
MSE
MAPE, %
MIPE, %

0.9366
0.724
12.88
5.17

0.9874
0.258
6.04
1.92

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481

In addition, the developed ANN model has lower calibration

errors.
(7) The developed procedure for this numerical modelling and
ANN system can be applied in other industrial process when
the mixture of CO2 H2 ONH3 urea includes chemical and
vapourliquid equilibrium under wide ranges of thermodynamics conditions.
NOMENCLATURE
Acronyms

Figure 16. Relative effects of important variables on CO2 conversion.

the magnitude of the dependent parameter. Clearly, the feed

temperature, as shown by T, is the most important parameter
affecting the amount of urea produced as an increase in the feed
temperature leads to an increase in the CO2 conversion. In addition, the impacts of NH3 /CO2 and H2 O/CO2 on the CO2 conversion
are in agreement with the published studies.[1,7,10,12] Increase in
NH3 /CO2 results in an increase in the value of amount of produced urea. As the H2 O/CO2 increases, the magnitude of the CO2
conversion decreases.

ANN
BP
CSTR
EOS
MAPE
MIPE
MLP
MSE

Variables
Ai
aij
B3,1
b
CA
CT

CONCLUSIONS
A mathematical model and an ANN system were developed to simulate the urea synthesis reactor of Shiraz Petrochemical Company.
Combination of thermodynamics and reaction frameworks were
employed in the present numerical simulation. Then, an optimisation study was conducted. The following conclusions can be
drawn based on the results of this study:
(1) An arrangement of CSTRs in series was used during this simulation study to predict the non-ideal hydrodynamic behaviour
of the reactor. It was found that 12 CSTRs can suitably model
the synthesis reactor.
(2) The reaction of the urea synthesis is generally exothermic
and the temperature increases along the reactor from the feed
stage to the product stage. As a result, the flow rates of urea
and H2 O increase with consumption of the key reactants that
contain NH3 and CO2 .
(3) Simulation results and ANN predictions compared against
actual operation data show a reasonable agreement between
the calculated and measured values of the components flow
rates, urea conversion and temperature.
(4) The preferred temperature of 191 C, and a pressure of 132 bar
were determined as the optimum values of T and P to attain
a maximum conversion of CO2 to produce urea.
(5) A parametric sensitivity analysis using the ANOVA technique
indicated that the feed temperature is the most important
factor affecting the CO2 conversion for urea formation.
(6) The ANN model is more precise and faster than the mathematical method in use for predicting the thermodynamic
and synthesis behaviour of urea reactor, especially when the
experimental information is limited. The average absolute relative error with ANN for the test data was obtained to be
2.35, while this value is 9.47 for the mathematical model.

482

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

Artificial Neural Network

back propagation
continuous stirred tank reactor
equation of state
maximum absolute percentage error
minimum absolute percentage error
multiple layer perceptron
mean squared error

Ci,r
CPmean,i
E
Fi
fi0
G
g
H i
HJi
Kr
KHi,j
k
Mi
mi
Ni
n
P
Pisat
Qf
J
Q
qi
R
R2
Ri
ri
T
V
vi

constants of fugacity equation for ammonia

UNIQUAC binary interaction parameters between components i and j
interaction effect between components 1 and 3
closest distance between the ions (cm)
concentration of component A in a mixture (mol/m3 )
total concentration of components in a reaction mixture
(mol/m3 )
coefficients of Equation (25)
mean heat capacity of the component i at a constant
pressure
activation energy of reaction (J/mol)
molar feed flow of the component i in the feed stream
(mol/s)
standard fugacity of component i as pure liquid at zero
pressure (atm)
Gibbs free energy
acceleration due to gravity (m/s2 )
partial molar enthalpy of component i (J/mol)
total enthalpy of component i in the element J (J/mol)
chemical equilibrium constant of reaction r
Henrys constant of component i in solvent j
reaction constant
molecular weight of component i (g/mol)
molality of component i in liquid solution (g solute/
1000 g solvent)
number of moles of component i
number of CSTRs
absolute pressure (atm)
vapour pressure of component i (atm)
volumetric flow rate of feed (m3 /s)
rate of heat transfer to/from element J (J/s)
area parameter of component i in UNIQUAC model
gases constants (atm m3 /mol K)
coefficient of determination in statistical analysis
reaction rate of component i (mol/s)
volumetric parameter of component i in UNIQUAC model
absolute temperature (K)
volume of reactor/condenser/stripper (m3 )
molar volume of component i in liquid phase (m3 /mol)

VOLUME 92, MARCH 2014

vi
uji
X
xi
yi
Z
z

molar volume of component i in dilute liquid solution

phase (m3 /mol)
a parameter in UNIQUAC model which resembles the
interaction parameter of components i and j
matrix of mole fractions in liquid phase
molar fraction of component i in liquid phase
molar fraction of component i in gas phase
compressibility factor for gas phase
coordination number of the UNIQUAC model

APPENDIX A: MOLAR ENTHALPIES OF COMPONENTS

Partial molar enthalpies for H2 O (i = 1) and NH3 (i = 2) are
obtained through the relationship[21,22,30] :


H i (T, x) = Hi0 (T) RT 2


ri
ij
ij

i
i

i
i
i
 ij
r

stoichiometric coefficient of component i in reaction r

constant for intermolecular forces between the molecules
i and j
intermolecular forces between the molecules i and j
difference operator
activity coefficient of component i in liquid phase
activity coefficient of component i in liquid phase in case
of infinite dilution
surface area fraction of component i
volume fraction of component i
fugacity coefficient of component i in gas phase
interaction term of components i and j in UNIQUAC
model, exp( aij /T)
progress degree of reaction r

ln fi0
T


H 3 (T, x) = H30 (T) RT 2

combinatorial
DebyeHuckel
energy
gas phase
liquid phase
model
predicted
residual
reaction


(A.2)

ln 3
T


(A.3)

H 30 (T) as a reference enthalpy is expressed as follows[21,22,30] :


C
DH
E
g
l
M
P
R
r

(A.1)

Hi0 (T) in Equations (A.1) and (A.2) is the molar enthalpy of a

hypothetical liquid and Hi (T) is the molar enthalpy of a pure component at ideal gas condition, but zero pressure and the system
temperature.
For CO2 (i = 3), the reference state is assumed to be a very dilute
solution in water and its partial molar enthalpy is calculated by
the following expression[21,22,30,40] :

H 30 (T) = H 3 (T) RT 2

Superscripts

Also, Hi0 (T) in the above equation is computed using the following equation[21,22,30] :
Hi0 (T) = Hi (T) RT 2

Greek Symbols

ln i
T

ln KH3,1
T


(A.4)

In the above equation, KH3,1 is the Henrys constant of CO2 in

water which is obtained as follows[21,22,30] :
ln KH3,1 = ln 3 (T) + ln f30 (T)

(A.5)

where 3 is the activity coefficient of CO2 when its concentration

approaches to zero. This parameter is calculated by[21,22,30] :
ln 3 =

a31
q3 31 + C3
T

(A.6)

Subscripts
A
cond
e
f
g
i
J
l
m
strip

component A
condenser
exit stream
feed stream
gas phase
component i
volumetric element J
liquid phase
mixture
stripper

ACKNOWLEDGEMENTS
The authors would like to acknowledge the Shiraz Petrochemical Company (SPC), Petrochemical Research and Technology
Company (NPC-RT) and Chemical and Petroleum Engineering
Department of the Shiraz University for providing the required
data and support throughout this study. The financial support
of the Mitacs Elevate and the Natural Sciences and Engineering Research Council of Canada (NSERC) for this research is also
appreciated.

VOLUME 92, MARCH 2014

All parameters except C3 in Equation (A.6) are known. C3 is

a constant for each component and assumed to be zero for CO2
component.
To estimate the partial molar enthalpies of the other components, the following general formula is used[21,22,41] :


H i0 (T, x) = H i0 (T) RT 2

ln i
T


(A.7)

H i0 (T) is the molar enthalpy of component i at standard conditions.

Anions and cations formed in the solution are not in neutral
charge conditions. Therefore, it is not possible to predict their
concentrations, independently. To tackle this issue, anions and
cations are considered as dual combinations in order to determine their molar enthalpies. Thus, the ionic molar enthalpies of
ammonium (i = 4), bicarbonate (i = 5) and carbamate (i = 6) are
computed using the following formulas[22,30,40] :


0
(T) RT 2
H 4,5 (T, x) = H 4,5

ln 40
T


+

ln 50
T



THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

(A.8)

483


0
(T) RT 2
H 4,6 (T, x) = H 4,6

ln 40
T


+

ln 60
T


(A.9)

APPENDIX C: MODEL EQUATIONS FOR CONDENSER AND

STRIPPER
The main equations to simulate the condenser are as follows:

0
H 4,5
(T) = H 40 (T) + H 50 (T)

(A.10)

0
(T) = H 40 (T) + H 60 (T)
H 4,6

(A.11)

Following the Vant Hoff approach, molar enthalpies of components at reference states are as follows[21,22,30] :


0
H 4,6
(T) = 2H20 (T) + H 30 (T) + RT 2

ln K1 (T)
T

Rr=4
Fi,in Fi,out = Vcond r=4
i


(A.13)

Consequently, molar enthalpy of urea can be presented

as[21,22,41] :

ln K3 (T)
T

H 70 (T) = H10 (T) + 2H20 (T) + H 30 (T) + RT 2

(C.1)


(A.14)

where Vcond is the volume of the condenser. Fi,in and Fi,out are
the molar flow rates of component i entering and exiting the
condenser, respectively.
It should be noted here that just NH3 (2), CO2 (3), NH+
4 (4) and
H2 NCOO (6) are available in the condenser. Also, the only reaction occurred in the condenser is the formation of ammonium
carbamate (r = 4).
- One equation for the energy conservation in the condenser is
expressed as:

l
l
Fi,in
Hi,in
+

The enthalpy of the liquid mixture is obtained as follows:

i = 2, 3, 4, 6

(A.12)

ln K2 (T)
T

0
(T) = H10 (T) + H20 (T) + H 30 (T) + RT 2
H 4,5

- Two equations for the phase equilibrium of NH3 (2), CO2 (3):
g
fi = fil (i = 2, 3). It is acceptable to assume that no water exists
in the tube part of the condenser.
- Four equations for the material balance of NH3 (2), CO2 (3),

NH+
4 (4) and H2 NCOO (6) are written as the following:




Fi,in H i,in

l
l
Fi,out
H i,out

g
g
w
Fi,out H i,out = Q

(C.2)

H(T, x) =

xi H i (T, x)

(A.15)

i=1

xi is the molar fraction of component i in the liquid mixture and

n is the number of components.
The enthalpies of gas phase components are determined
by[21,22,41] :
ig

Hi (T) = H0 + CPmean,i (T T0 ) + HiR

(A.16)

ig

H0 is the enthalpy of component i at ideal gas state condition at

temperature T0 and pressure P0 as reference conditions. CPmean,i
is the mean heat capacity of component i at a constant pressure
in the temperature range of T and T0 . HiR is the residual (excess)
enthalpy of the component i which shows the difference between
enthalpies of component i at ideal and non-real states.

w represents the enthalpy change of the water phase in

Here, Q
the shell.
According to the process design of the stripper, the chemicals

in the stripper include NH3 (2), CO2 (3), NH+

4 (4), and H2 NCOO
(6), H2 NCONH2 (7), and H2 NCONHCOH2 N (8). Thus, the same
thermodynamic equilibrium equations are written for ammonia
and carbon dioxide. Also, the material balance for the above components is as follows:
Fi,in Fi,out = Vstrip

ln iC (x)

and ln iR (T, x)

[21,22,29]

Based on the UNIQUAC model, the

are determined by the following expressions

ln iR (T, x) = qi


ln

j=1

i ij

values

n



j
ij


1+

n

j=1

k kj

(B.1)

 

i
= ln
xi

z

 

i
qi ln
2
i

+ li

 
n
i
xi

xi li

j=1

z is the coordination number of the UNIQUAC model.

484

i = 2, 3, 5, 6, 7, 8

(C.3)

l
l
Fi,in
Hi,in
+




Fi,in H i,in

l
E
Fi,out
H i,out

g
g
s
Fi,out H i,out = Q

(C.4)

k=1

ln iC (x)

ri Rr

where Vstrip stands for the volume of the stripper.

Similar energy conservation equation should be written for this
process element as below:


APPENDIX B: ACTIVITY COEFFICIENT OF LIQUID
COMPONENTS

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

(B.2)

s shows the enthalpy change of the

In the above equation, Q
steam phase.
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