Open Chemistry 2022; 20: 424–430
Research Article
Rommel Ortiz Guzmán*, Antonio Bueno Lazo
Simulation of a reactor considering the
Stamicarbon, Snamprogetti, and Toyo patents
for obtaining urea
https://doi.org/10.1515/chem-2022-0157
received January 24, 2022; accepted April 15, 2022
Abstract: In the present work, the plug flow reactor of
a urea production plant from ammonia produced from
natural gas of the Camisea fields (Peru) was designed,
comparatively analyzing three commercial processes
currently in operation: Stamicarbon, Snamprogetti, and
Toyo. ASPEN PLUS software was used as a simulation
tool. To carry out the simulation and subsequent compar-
ison of the three urea production patents, it will start from
the same feed of ammonia (37,851 kmol/day) and carbon
dioxide (18,989 kmol/day) for the three cases. For the
design of urea synthesis reactors, reactors of the same
size (2.3 m diameter and 29 m length) were designed. The
results are graphs that illustrate the variation of the length
of the reactor with the reaction temperature, the variation
of the length of the reactor with the residence time, and the
variation of the conversion with the time for each patent.
Keywords: urea, reactor design, process simulation,
ASPEN PLUS
1 Introduction
Urea is not only the most produced and used chemical
fertilizer in the world but also a multipurpose raw mate-
rial [1,2]. Since the 1930s and 1940s, urea production has
been a major topic among industry researchers [3]. Faced
with an increasingly severe energy crisis and a deterior-
ating environment, researchers continue to analyze their

* Corresponding author: Rommel Ortiz Guzmán, Department of
Petrochemical Processes, Faculty of Chemistry and Chemical
Engineering, National University of San Marcos, Lima, Peru,
e-mail: rommel.ortiz@unmsm.edu.pe
Antonio Bueno Lazo: Department of Separation Processes, Faculty
of Process Engineering, National University San Antonio de Abad of
Cusco, Cusco, Peru
Open Access. © 2022 Rommel Ortiz Guzmán and Antonio Bueno Lazo, published by De Gruyter.
Commons Attribution 4.0 International License.
production process in order to reduce energy consumption
and obtain cleaner production; that is why process simula-
tion is the primary computer technology for the analysis of
process design decisions and their optimization [4]. In addi-
tion, the energy demands and environmental challenges for
its processing are high, which is why the need for optimiza-
tion and energy conservation has increased interest in the
simulation of plants that produce the said product [5]. More
research is currently required in order to solve the industrial
challenges that make it difficult to select a more sustainable
process design. In previous works, the simulation of urea
processes has been developed. However, a limited number
of them have been implemented, because the parameters of
their quality have not been considered, with the severe oper-
ating conditions of the process and the lack of information
being the main challenges in the modeling and simulation of
such a complex process [6]. Urea production patents (Sta-
micarbon, Snamprogetti, and Toyo) differ on the separation
and recycling of ammonia and carbon dioxide. The optimi-
zation of these production technologies aims to maximize
the conversion of carbon dioxide and the optimization of
heat recovery [7].
Zhang and Yao studied the fluid dynamics of a urea
reactor considering a gas–liquid fluid reactor model, in
which perforated plates are installed to avoid counter
mixing, defining a thermodynamic model, reaction kinetics,
and dynamics of fluids and solving the urea reactor model
defined by a series of non-linear equations by a numerical
method, the solution of which illustrates the whole tem-
perature profile and the concentrations of each component
within the reactor. The results of the model were in good
agreement with the design data [8].
Rasheed simulated the urea reactor by applying the
SR-POLAR equation for the thermodynamic model and
proposed a kinetic power model for the formation of
ammonium carbamate and urea. The deviations from
the industrial data were recorded to be less than 5.0%
for the liquid composition at the outlet of the reactor [9].
Zendehboudi et al. proposed a mathematical model
for a urea reactor based on the UNIQUAC model; when
This work is licensed under the Creative
 Simulation of a reactor considering the Stamicarbon, Snamprogetti, and Toyo patents for obtaining urea
comparing the results of the model with the industrial
data, a standard deviation of less than 2.3% was obtained
for the liquid outlet stream [10].
Nawaz evaluated different processes to produce ammo-
nium sulfate and urea with a ratio of 60/40, respectively,
from ammonia, whose feed was 550,000 ton/year. It is
concluded that the most profitable route to comply with
the urea plant design from carbon dioxide was using the
Snamprogetti process and ammonium sulfate from sul-
furic acid. The mechanical and chemical design of the
urea reactor was proposed, determining the following vari-
ables: a volume of the pseudo-first-order isothermal plug
flow reactor (PFR) of 145.5 m3, a diameter of 2.61 m, a
reactor thickness of 100 mm, and a residence time of
16.71 s. A “half-pipe”-type cooling jacket was used to
maintain the isothermal conditions of the reactor [11].
Baboo developed a kinetic model for the synthesis of
urea from ammonia and carbon dioxide, in which he
demonstrated the possibility of increasing the efficiency
of the reactor. The optimization of the carbon dioxide
conversion is determined by the reduction of energy
consumption and recycling and by the increase in the
production using the same reactor. The design of the
high-efficiency trays in the reactor was developed through
the fluid dynamics simulation and the modeling of the
physical–chemical equilibria and the heat transfer phe-
nomena, the main one being the reduction of the specific
consumption of steam, obtaining reductions of the same
amount of 250–300 kg/ton urea and an increase in the
capacity of the reactor of 10–20% [12].
Sikder et al. designed a simulation of the Stamicarbon
urea production process using the Aspen HYSYS v.7.1 plat-
form to investigate the effect of operating parameters:
carbon dioxide temperature, high-pressure (HP) steam
temperature, and low pressure (LP) steam, depending
on the composition of urea; the following results were
obtained: at a range of 357–365°C of HP steam tempera-
ture, the 0.055–0.08 urea composition was obtained; at a
range of 287–316°C of LP vapor temperature (low pres-
sure), the 0.055–0.782 urea composition was obtained.
The heat generated in the urea solution decreased with
increasing CO2 temperature and increased with increasing
CO2 pressure. The CO2 conversion in the reactor was con-
stant at pressures greater than 210 atm, which was also
determined at an NH3/CO2 ratio of 15 [13].
Mane et al. studied the conversion and optimization
of the urea reactor by analyzing process parameters such
as NH3/CO2 ratio, pressure, and temperature and con-
cluded that these factors intervene in increasing its pro-
duction by reducing the specific volume of the reactor. The
number of trays in the reactor was increased; however, its
 425
efficiency was not increased. By modifying the NH3/CO2
feed ratio of the reactor feed, the efficiency of the reactor
was increased. From the experimental data, it was con-
cluded that by varying the value of the NH3/CO2 ratio
between 3/1 and 3/4, the maximum value of the urea
reactor efficiency was obtained [14].
Yoke and Mahadzir proposed mathematical models
for the synthesis of urea and ammonia, determining that,
for the urea synthesis reaction at optimal operating con-
ditions of 450 K and 12 MPa, the equilibrium carbon
dioxide conversion, the maximum molar flux of urea,
and its equilibrium concentration were 79%, 410 mol/s,
and 750 mol/m3, respectively. The optimal range of the
NH3/CO2 feed ratio was 2–3.5. For the ammonia synthesis
reaction at optimal operating conditions of 660 K and
23 MPa, the equilibrium nitrogen conversion, the ammonia
molar flux, and its equilibrium concentration were 27.5%,
420 mol/s, and 300 mol/m3, respectively. The mean per-
centage error for the equilibrium nitrogen conversion
and the equilibrium ammonia molar flux were 6.154
and 5.932%, respectively, compared to the published
data at industrial plant conditions [15].
In this research work, the design and characteriza-
tion of the PFR of a urea production plant from ammonia
produced from natural gas from the Camisea fields (Peru)
was proposed, which was defined with the same dimen-
sions for each urea production patent (Stamicarbon,
Snamprogetti, and Toyo), carrying out the analysis of
residence time, length reactor, temperature, and conver-
sion. The results are graphs that illustrate the variation of
the length of the reactor with temperature, the variation
of the length of the reactor with the residence time, and
the variation of the conversion with the residence time for
each patent.
2 Materials and methods
2.1 Thermodynamic package
The modeling of the thermodynamic properties of the
ammonia–carbon dioxide–water–ammonium carbamate–
nitrogen–oxygen system is based on the SR-POLAR model
[16] within ASPEN PLUS, which uses an equation of state
suitable for high pressure and temperature conditions of
urea synthesis.
The equation for the model is
RT a
p= − , (1)
v−b v (v + b )
426  Rommel Ortiz Guzmán and Antonio Bueno Lazo

1 (RTc)2 2.2 Chemical kinetics of reactions

a= α(Tr ) , (2)
9(21 / 3 − 1) Pc
The two main reactions take place in the urea synthesis
21 / 3 − 1 RTc
b= . (3) process:
3 Pc
(1) 2NH3 +  CO2  → NH2COONH4
The temperature dependence of α is given by the (2) NH2 COONH4 → Urea + H2 O
following expression, which is a generalization of the
correlation already proposed by Mathias [17] The first reaction, which takes place in the liquid
0.5
phase, converts ammonia and carbon dioxide into ammo-
⎧ [1 + m(ω)(1 − Tr ) − p1 (1 − Tr )(1, Tr < 1,
nium carbamate and is very exothermic and fast. The che-
⎪
α(Tr ) = + p2 Tr + p3 Tr2 )]2 (4) mical equilibrium is obtained at the operating conditions
⎨
⎪ {exp[c (1 − Trd )]} 2 , Tr > 1. of the reactor. The second reaction also takes place in the
⎩
liquid phase and is endothermic; its speed is slow, and
With equilibrium is not normally reached in the reactor.
m (ω ) Equilibrium has been described in terms of fugacity
d=1+ − p 1 (1 + p 2 + p 3 ) ,
2 coefficients since an equation of state is used as a thermo-
dynamic model. The equilibrium constant for Reaction
1
c=1− , (1), in terms of mole fractions, is written as follows:
d
0 0 0 2
m(ω) = 0.48508 + 1.55191ω − 0.15613ω 2 . ⎧ −(GCarbamate − 2GNH3 − 2G CO2 ) ⎫⎛ P ⎞ ⎡ ϕNH3ϕCO2 ⎤
2
K1 = exp . (12)
⎨ RT ⎬⎝ P 0 ⎠ ⎢ ϕCarbamate ⎥
⎩ ⎭ ⎣ ⎦
Parameters p1, p2, and p3 can be either fitted to experi-
mental vapor pressures or derived from the Antoine para- The equilibrium constant for Reaction 1 in terms of
meters of the pure components. They are set to zero for mole fractions is as follows:
nonpolar molecules. xcarbamate
Mixing rule: K1 = 2
. (13)
xNH x
3 CO2
It is suggested to use a linear mixing rule for b and a
“pseudo-quadratic” mixing rule for a: Similarly, equilibrium equations are developed for Reaction 2.
Reaction rates 1 and 2, in units of kmol/s m3, are as follows:
bmix = ∑bixi, (5)
i xcarbamate ⎫
n n
Rate1 = k1 ⎧xNH
2
x −
3 CO2
, (14)
⎨
⎩ K1 ⎬
⎭
amix = ∑∑ aijxixj , (6)
i=1 j=1 xUrea ⋅ xH2O ⎫
Rate 2 = k2 ⎧xcarbamate − . (15)
where ⎨
⎩ K2 ⎬
⎭

aij = (aiaj )0.5[1 − Kij (T , x¯ )]. (7) The two velocity equations have been formulated so
that they reach equilibrium at long residence times. The
Schwartzentruber and Renon proposed the following rate constant for Reaction (1) (k1) is set to a large value so
equation (8) to calculate Kij (x ): that it is in equilibrium. The rate constant for Reaction (2)
mij xi − mjixj determines the conversion of urea in the reactor. Only
Kij (x ) = kij + lij (xi + xj ) , (8)
mij xi + mjixj scant information is available to determine k2 and it is
generally advisable to adjust its value to fit the plant data.
where
An approximation for k2 is the following:
kji = kij, lji = −lij , 6
(9) 15 × 108 e(−(100 × 10 ) / RT ) (16)
mji = 1 − mij , kii = lii = 0, k2 = .
v
k ij(2) lij(2)
kij = k ij(0) + k ij(1)T + , lij = k ij(0) + lij(1)T + , (10)
T T 3 Results and discussion
1⎡ ⎛ (0) mij(2) ⎞⎤
mij = ⎢1 + tanh ⎜mij + ⎥. (11) Simulations were carried out from the same feed of
2⎢ T ⎟⎥
⎣ ⎝ ⎠⎦ ammonia (37,851 kmol/day) from natural gas from the
 Simulation of a reactor considering the Stamicarbon, Snamprogetti, and Toyo patents for obtaining urea  427

Table 1: Urea synthesis reactor dimensions Table 2: Operating conditions of the reactors of each patent

Diameter (m) Length (m) Patent Temperature Pressure

(°C) (atm)
2.3 29
Urea reactor Stamicarbon 166 136.46
Urea reactor Snamprogetti 166 170.11
Urea reactor Toyo 167 238.16
Camisea fields and carbon dioxide (18,989 kmol/day) for
each patent (Stamicarbon, Snamprogetti, and Toyo), fol-
lowed by a subsequent comparison of the three urea pro-
reactor increases, the length section corresponds to a
duction technologies. For the design of urea synthesis
linear function (which is seen in greater detail in the
reactors, PFRs of the same size (because of having the
Toyo patent). In addition, a higher reaction temperature
same feed and because the same chemical reactions
of 190°C is obtained for the Snamprogetti patent, which
involved in the entire process) but with different oper-
implies higher energy requirements on its part; on the
ating conditions (defined by each patent), were selected.
other hand, almost similar results are obtained for the
The dimensions of the reactor were calculated, as
Stamicarbon and Toyo patents, which are 183 and 182°C
shown in Table 1.
respectively.
Nawaz, from an ammonia feed of 250,000 ton/year,
Table 3 illustrates the maximum reaction tempera-
obtained a PFR volume of 145.5 m3 and a diameter of
tures of each patent.
2.61 m (corresponding to a length of 27.2 m), with very
similar results to those obtained in the present study [11].
The dimensions of the reactors shown in Table 1 will
be the same for each patent, each one will be analyzed 3.2 Analysis of the reaction residence time
below. with respect to the length of the reactor

Figure 2 shows the progression of reaction residence time

with respect to the reactor length in the Stamicarbon,
3.1 Analysis of the reactor temperature with Snamprogetti, and Toyo patents.
respect to its length
Table 3: Maximum reaction temperature of each patent
Figure 1 shows the variation of the reactor temperature
with respect to its length in the Stamicarbon, Snampro-
Patent Temperature reaction
getti, and Toyo patents. (°C)
Table 2 illustrates that in all the patents for obtaining
Urea reactor Stamicarbon 183
urea, the reactors operate at the same temperatures. In
Urea reactor Snamprogetti 190
addition, in Figure 1, as the operating pressure of the Urea reactor Toyo 182

Stamicarbon Snamprogetti Toyo Stamicarbon Snamprogetti Toyo

195 1.4

190 1.2
TEMPERATURE (°C)

185 1
TIME (HOUR)

180 0.8

175 0.6

170 0.4

165 0.2

160 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
REACTOR LENGTH (METER) REACTOR LENGTH (METER)

Figure 1: Reactor length (m) vs temperature (°C). Figure 2: Residence time (h) vs reactor length (m).
428  Rommel Ortiz Guzmán and Antonio Bueno Lazo
Table 4: Residence time of the reactor of each patent
Patent
Urea reactor Stamicarbon
Urea reactor Snamprogetti
Urea reactor Toyo
Table 2 shows that in all the patents for obtaining
urea, the reactors work at the same pressures.
In Figure 2, it is determined that the higher the oper-
ating pressure, the lower the inflection point of the graph
(which corresponds to a lower volume range of the
reactor); in turn, it will generate a longer residence time.
Table 4 illustrates the residence times of the reactors
for each patent.
3.3 Comparison of patents
Peruvian State has an average demand for urea of 400 kton/
year, which is why, for this purpose, it was decided to
evaluate each patent to obtain the said production.
It was determined that the feeds of ammonia and
carbon dioxide required for this purpose are 235.45 and
305.24 kton/year, respectively, which correspond to the
feed flows of the patent with the highest conversion,
which is Toyo; this is shown in Figure 3.
Table 5 shows a summary of the yields of granulated
(solid) urea from ammonia obtained from natural gas.
From Table 5, it can be deduced that the Toyo patent
obtains the highest production of urea (414.95 kton/year)
from the same supply of ammonia and carbon dioxide;
this is due to the fact that the reactor operates at a higher
pressure (which is illustrated in Table 2), obtaining a
higher conversion (60%), which is illustrated in Figure 3.
Toyo Snamprogetti
0.7
0.6
0.5
CONVERSION CO 2
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3
TIME (H)
Figure 3: CO2 conversion vs time (h).
Table 5: Summary of urea production of the three patents
Residence time (h) Feed Product (kton/year)
(kton/
0.42
year)
0.72
Toyo Stamicarbon Snamprogetti
1.37
Ammonia 235.45 — — —
Carbon 305.24 — — —
dioxide
Solid urea — 414.95 387.29 276.63
When comparing the reactors for the three patents for
the production of urea previously mentioned, Figure 3 is
obtained.
Figure 3 shows that when comparing the Toyo patent
at the same reactor residence time, for example, at 0.42 h
(which is the residence time of the Stamicarbon patent,
which is the minimum with respect to the three patents),
it has the highest CO2 conversion (60%) compared to the
Snamprogetti and Stamicarbon patents. This difference in
conversions is related to the difference in energy require-
ment downstream of the respective reactors. A higher
conversion of CO2 determines a lower energy consump-
tion in the decomposition process of the non-reactive
material.
Binti [18] and Ali and Anantharaman [19] obtained
that the conversion of CO2 in the urea reactor was 60%;
the conversion obtained by Wang and Li was 58.99%
[20]; similar results were obtained in the present research
work. The aforementioned authors compared their results
with real plant data, obtaining an excellent fit (error ± 5%).
In the present study, the SR–POLAR thermodynamic
model was used because several authors such as Zahid
et al. [5] and Rasheed [9] recommended it for its great
adjustment to the thermodynamic system of the present
study; however, Ali and Anantharaman used the SRK
thermodynamic model, obtaining the same result [19],
which shows that this model is also applicable. This
Stamicarbon
result is also the same as predicted by the licensor of
the Toyo patent. Yoke Yi and Mahadzir obtained a con-
version of carbon dioxide in an equilibrium of 79% [15];
it is very likely that the error they made in their calcula-
tions is in the selection of the thermodynamic model,
because they do not specify it in their research.
0.4 0.5
4 Conclusion
The present work developed the design of a reactor for a
400 kton/year urea production, showing that the Toyo
 Simulation of a reactor considering the Stamicarbon, Snamprogetti, and Toyo patents for obtaining urea  429

patent is the one that obtains the highest conversion
(60%), which translates into a lower energy requirement.
This result will be obtained independently of the supply
of ammonia and carbon dioxide, because the sequence of
operations and unit processes of each patent will always
be the same for each simulation that is carried out.
for Scientific, Technological Development and Technological
Innovation (FONDECYT), nowadays PROCIENCIA, one of
the ten doctoral programs subsidized by PROCIENCIA in
Peru – Contract 04-2018-FONDECYT/BM. The authors, there-
fore, acknowledge with thanks DSR for technical and finan-
cial support.

Funding information: The results presented are part of the

doctoral research project sponsored by the National Fund for
Nomenclature Scientific, Technological Development and Technological
Innovation (FONDECYT), nowadays PROCIENCIA, one of
a attraction parameter (Pa m6/mol2) the ten doctoral programs subsidized by PROCIENCIA in
aij calculation parameter to determine amix Peru – Contract 04-2018-FONDECYT/BM. The authors, there-
(Pa m6/mol2) fore, acknowledge with thanks DSR for technical and finan-
amix mix attraction parameter (Pa m6/mol2) cial support.
b repulsion parameter (m3/mol)
bmix mix repulsion parameter (m3/mol) Author contributions: Rommel Ortiz Guzmán – Conceptualiza-
c,d pure-component parameters (for super- tion, data curation, formal analysis, funding acquisition,
critical temperatures) investigation, resources, visualization, writing-original
Gi0 Gibbs free energy of the ideal gas of draft; Antonio Bueno Lazo – Methodology, project admin-
component i for T, P° (J/mol) istration, software, supervision, validation, writing-review
Kij calculation parameter to determine aij and editing.
kij, lij , mij parameters of the mixing rule
k ij(0), k ij(1), k ij(2) parameters for the temperature depen- Conflict of interest: The authors declare no conflict of
dence of kij interest.
lij(0), lij(1), lij(2) parameters for the temperature depen-
dence of lij Ethical approval: The conducted research is not related to
mij(0) , mij(2) parameters for the temperature depen- either human or animal use.
dence of mij
m (ω ) acentric factor-dependent function Data availability statement: All data generated or ana-
p1,p2,p3 pure-component parameters in the lysed during this study are included in this published
equation of state article.
P pressure (Pa)
P0 reference pressure (1.01325 × 105 Pa)
Pc critical system pressure (Pa)
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