HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY

OFFICE FOR INTERNATIONAL STUDY PROGRAMS

FACULTY OF CHEMICAL ENGINEERING

DESIGN OF FLUID – FLUID REACTION EQUIPMENT

UREA SYNTHESIS REACTION

Course: Reaction Engineering

Class: CC01 – Group 07
Lecturer: Dr. Tran Tan Viet

Member List
Full name Student ID
Nguyễn Ái Minh Châu 2252089
Huỳnh Ngọc Hân 2252198
Đinh Nguyễn Phương Nghi 2252515
Nguyễn Ngọc Như Quỳnh 2252704
Trương Hữu Tài 2252729
 TABLE OF CONTENTS
1. INTRODUCTION.....................................................................................................................2
1.1. Type of Reaction: Heterogeneous – Fluid-Fluid Reaction.....................................2
1.2. Reaction Equipment................................................................................................4
1.3. Reactions: Mechanism, Reaction Types, and Kinetics...........................................4
2. KINETICS.................................................................................................................................6
2.1. Study of chemical kinetics of urea synthesis from CO2 absorption in aqueous NH3
solutions 6
2.2. Development of the rate expression model for urea production from extent of reaction. .10
2.3. Determination of rate constants and equilibrium constants...............................................14
3. REACTORS............................................................................................................................18
3.1. Descriptions of reactors.....................................................................................................18
3.2. Determination of the optimal kinetic parameters from the application of optimization
model 18
3.3. Development of the transient mole fraction and temperature models of the urea reactors19
3.4. Input parameters for simulation.........................................................................................22
3.5. Results and discussion.......................................................................................................23

1
1. INTRODUCTION

Urea (chemical formula: NH₂CONH₂) is one of the most important petrochemical

products, primarily utilized as a nitrogen fertilizer in agriculture. It is synthesized on an
industrial scale by the reaction between ammonia (NH₃) and carbon dioxide (CO₂) under
conditions of high pressure (13–35 MPa) and high temperature (170–200°C).

There are several commercial processes for the production of urea, generally
classified into once-through, partial recycle, and total recycle processes. Among them, the
total recycle process is the most widely adopted in industry, where all unconverted ammonia
is recycled back into the reactor, achieving an overall ammonia conversion efficiency of
approximately 99%.

The synthesis of urea involves two main chemical reactions:

1. Formation of ammonium carbamate through the reaction of ammonia and

carbon dioxide.
2. Dehydration of ammonium carbamate to produce urea and water.

Traditionally, it was assumed that the formation of ammonium carbamate occurs

entirely within the liquid phase. However, recent modeling approaches, such as the one
discussed in the current study, suggest that the reaction is heterogeneous—taking place
between gas-phase reactants (NH₃ and CO₂) and forming a liquid-phase product
(NH₂CO₂NH₄).

1.1. Type of Reaction: Heterogeneous – Fluid-Fluid Reaction

A heterogeneous fluid-fluid reaction is a type of chemical reaction where the

reactants are in different fluid phases—typically gas and liquid—and the reaction takes
place at the interface between these phases. In such systems, the overall reaction rate is
often influenced not only by chemical kinetics but also by mass transfer processes, as one or
more reactants must diffuse across the phase boundary to participate in the reaction. This

2
distinguishes them fundamentally from homogeneous reactions, where all reactants are in a
single phase—either all gases, all liquids, or all solids dissolved uniformly in a solution—
and thus react throughout the entire volume without phase boundaries.

One prominent industrial application of heterogeneous fluid-fluid reactions is in urea

production. In the synthesis process, gaseous ammonia (NH₃) and carbon dioxide (CO₂) are
introduced into a high-pressure reactor where they react to form ammonium carbamate
(NH₂CO₂NH₄), which is a liquid-phase product. Because the reactants are in the gas phase
and the product is in the liquid phase, this step qualifies as a gas-liquid heterogeneous
reaction. This initial formation of ammonium carbamate is exothermic and occurs rapidly,
often treated as an equilibrium reaction. It is followed by a slower, endothermic dehydration
reaction in the liquid phase that converts ammonium carbamate into urea (NH₂CONH₂) and
water. The effectiveness of this process depends heavily on the interfacial contact between
the gas and liquid phases, the residence time, pressure, and temperature—all of which must
be carefully controlled in the reactor design.

Apart from urea synthesis, heterogeneous fluid-fluid reactions are extensively used in
various industrial fields. In petroleum refining, processes such as hydrocracking involve
gas-liquid reactions where hydrogen gas interacts with liquid hydrocarbons in the presence
of a solid catalyst. Catalytic converters in automobile exhaust systems are another example,
where gas-phase pollutants are converted into less harmful substances through reactions at
solid surfaces, although this includes both gas-solid and gas-liquid interactions. In
environmental engineering, gas-liquid scrubbers remove acidic gases such as SO₂ or CO₂
by absorbing them into alkaline liquid solutions, another typical example of heterogeneous
fluid-fluid chemistry.

When compared with homogeneous reactions, heterogeneous fluid-fluid reactions

exhibit distinct advantages and limitations. One key benefit is the ease of product
separation, especially when different phases allow for straightforward mechanical
separation (e.g., gas from liquid). Additionally, these reactions can be optimized to exploit
selective interfacial behavior or employ catalysts at the interface. However, their
performance is often constrained by mass transfer resistance, requiring specialized

3
equipment such as packed towers, tray columns, or stirred-tank reactors with enhanced
mixing to ensure sufficient phase contact. In contrast, homogeneous reactions generally
proceed faster due to uniform mixing and are easier to model kinetically, but they often
suffer from more complex downstream separation and recycling processes.

1.2. Reaction Equipment

In chemical engineering, the Continuously Stirred Tank Reactor (CSTR) and the
Plug Flow Reactor (PFR) are two essential reactor models. A CSTR maintains perfect
mixing, ensuring uniform composition and temperature throughout the reactor. Reactants
are continuously fed in and products removed at the same rate. While easy to operate and
control, a single CSTR often requires a large volume to achieve high conversion, especially
for first-order reactions.

A PFR, by contrast, assumes no back-mixing and a unidirectional flow of reactants

through a tubular reactor. Concentration and temperature change along the length of the
reactor. Because reactants enter at their highest concentration and react progressively, PFRs
typically offer higher conversion efficiency per unit volume than CSTRs and are well-suited
for gas-phase and high-throughput processes.

To improve conversion in CSTR systems, multiple reactors can be arranged in series.

In this setup, the outlet of one reactor feeds the next, creating a concentration gradient
across the system. As the number of CSTRs increases, the system behavior approaches that
of a PFR. This configuration balances the simplicity of CSTRs with improved performance.

In contrast, CSTRs in parallel divide the flow among multiple identical units
operating simultaneously. While this setup offers operational flexibility and redundancy, it
does not improve conversion efficiency like a series configuration does. Compared to both,
PFRs still offer the best conversion for many reactions, though they are less flexible and
more complex to control.

1.3. Reactions: Mechanism, Reaction Types, and Kinetics

The overall urea production process consists of three principal chemical reactions:

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(1) Formation of Ammonium Carbamate (Heterogeneous Reaction):

Mechanism: Fast, exothermic reaction between gaseous ammonia and carbon dioxide
forming a liquid phase product.
Equilibrium: Assumed to reach equilibrium at reactor outlet conditions due to high
residence times.
Kinetics: Reaction rate is fast enough to be treated as an equilibrium process in
modeling.

(2) Formation of Urea (Homogeneous Reaction in Liquid Phase):

Mechanism: A slow, endothermic dehydration reaction within the liquid phase.

Reaction Type: Homogeneous.
Kinetics: Rate-limited, requiring sufficient residence time. Modeled typically by a
first- or second-order kinetic expression.

(3) Formation of Biuret (Side Reaction, Homogeneous Liquid Phase Reaction):

5
 Mechanism: Slow and endothermic, occurring under conditions of high temperature,
high urea concentration, and low ammonia concentration.
Reaction Type: Homogeneous.
Kinetics: The formation of biuret is an undesired side reaction, and its kinetics are
crucial for process optimization to maintain biuret concentration at acceptable levels
(typically less than 1%).

2. KINETICS

2.1. Study of chemical kinetics of urea synthesis from CO2 absorption in

aqueous NH3 solutions

2.1.1. Gas/Liquid mass transfer

The approach used to replicate the experimental outcomes is based on the classical
heterogeneous model, which assumes isothermal and isobaric conditions in line with the
experimental setup. Driven by the concentration gradient, carbon dioxide diffuses from the
gas bubbles into the liquid phase. In order to model this phenomenon, the two films theory
is applied. Rigorously, the reactive absorption process should incorporate both the film and
bulk regions in each phase, along with the corresponding mass balance equations. Thus, the
dynamic variation of the species concentrations results in a system of partial differential
equations that takes into account the interface flow rate and the reactions taking place in the
liquid phase. This model must be complemented with the relevant boundary and initial
conditions, related to bulk concentrations, the interface equilibrium and the molar transfer
rate taking place at the gas/ liquid interface.

6
 Fig 1: Representation of the mass transfer process

However, the lack of experimental data on the time-dependent concentration profiles

within the film makes such a rigorous model unnecessarily complex. Therefore, in this
work, the CO2 molar flow rate (NCO2 ), through the gas/ liquid interface, is modelled by
considering the global mass transfer coefficient, K LCO2 and the enhancement factor, E, which
accounts for the impact of the chemical reaction on the mass transfer rate:

where (CCO2) is the carbon dioxide concentration into the liquid bulk and (C CO2* )
represents its equilibrium concentration while the surface where mass transfer occurs is
indicated by S.

7
 To accurately describe the capture process, ammonia losses should also be
considered and modelled via eq. (2):

(i) Henry constants

By relying on the Henry’s law, the equilibrium concentration (Ci* ) of the i th species
can be evaluated through eq. (3).

where P is the total pressure of the capture system, y i is the molar fraction of the ith
species within the gas phase and Hij is the Henry constant for the i th species in the jth
solvent.
The Henry constant of a specific gas is strictly dependent on solvent properties and
system temperature. Eqs. (4) and (5) show the correlations adopted to evaluate the Henry
constant of CO2 (HCO2H2O) and NH3 (HNH3H2O) in water, respectively as a function of
temperature:

(ii) Enhancement factor

The enhancement factor (E) is defined as the ratio of the absorption rate of a gas
component into a liquid in the presence of chemical reactions to the rate observed in the
absence of such reactions. However, there are no general analytical expressions for
calculating E that exist, as it is highly dependent on reaction kinetics, the physicochemical
properties of the species involved, and the specific reaction regime. In this work, the

8
approach proposed in the literature is taken into account where the Hatta number, Ha (eq.
(9)), and the enhancement factor infinite, E inf(eq. (10)), are obtained to firstly determine the
reactive regime occurring:

where kapp is the apparent kinetic constant of the reactive phenomena that determine
the CO2 consumption into the liquid phase , Di is the diffusion coefficient of the ith species
and NH3 is the ammonia stoichiometric coefficient in the reaction involving CO 2
consumption. Under the experimental conditions considered in this study, two different
regimes are possible, i.e. the pseudo first order one that occurs when ammonia is in excess
compared to CO2 and the fast intermediate regime that takes place when CO 2 accumulates in
the liquid phase. When the pseudo-first-order condition is met (3 < Ha≪Einf), the
enhancement factor can be computed through eq. (11):

As the process evolves, the absorption changes into the fast intermediate regime,
during which the enhancement factor can be approximate by the eq. (12):

9
2.2. Development of the rate expression model for urea production from extent of
reaction

The synthesis of urea involves an equilibrium reaction where NH 3 and CO2 combine
to form an intermediate compound known as ammonium carbamate. This compound
gradually dissociates, leading to the formation of urea and water in the solution. The rate
model is described as a function of the reaction extent (reaction coordinates), based on the
mass action law and thermodynamic models, which incorporate the van't Hoff equation and
fugacity functions to express the individual component rates for urea synthesis. The
synthesis reaction proceeds according to an equilibrium process

where, k1 is the rate constant for the forward reaction, k 2 is the rate constant for the
backward reaction, and k3 is the rate of reaction for the dissociation of ammonium
carbamate to yield urea and water.

Reaction (1) represents a consecutive reaction that is split into exothermic and
endothermic parts, which are detailed in reactions (2a) and (2b), respectively

It has been found that the rate of the formation of ammonium carbamate (reaction 2a)
is much faster than the rate of its dehydration (reaction 2b). In the first stage we have a rapid
synthesis process of NH4COONH2, the concentration of which in a very short time reaches
its maximum value, whereas the concentration of (NH4)2CO and H2O grow rather slowly. In
the second stage, the synthesis of (NH4)2CO takes place, which leads to a decrease of the
concentration of NH4COONH2 to an equilibrium value, whereas the molar concentration of

10
NH3 and CO2 do not undergo any essential changes. The first stage is the shorter the
quicker the reaction (2a) in relation to reaction (2b).
As the result, the overall reaction rate was investigated through stage II, where the
total change in heat of reaction equalled - 33 kcal/mol, derived from the Individual heat of
reactions of Hr = -38.5kcal/mol and Hr = + 5kcal/mol in reactions (2a) and (2b),
respectively. The algorithm the development of the rate expression are as follows:

(1) The rates of carbamate and urea formation (reactions 2a and 2b) are expressed in
terms of relative reaction rates, following the principle of mass action, described in
equations (13a) and (13b), respectively

where, (-r1) is the rate of depletion of ammonia, (-r 2) is the rate of depletion of CO2
and (-r3) is the rate of formation of ammonium carbonate.

where (-r3) is the rate of dissociation of ammonium carbamate, (-r4) is the rate of
formation of urea, and (-r5) is the rate of formation of water. Equations (13a) and (13b) are
combined to obtain the overall rate of urea formation as follows:

where (-r3)t is the overall rate of ammonium carbamate formation, (-r3)1 the rate of
formation of ammonium carbamate from the exothermic equilibrium reaction (2a)), and (-
r3)2 is the rate of dissociation of ammonium carbamate from the reaction (2b).

11
 (ii) CO2 is the limiting reactant as the reaction stops immediately its amount is
finished within the reactor and expresses the rate of formation of ammonium carbamate and
urea in terms of concentrations of the reactants gives equations (14a) to (14d) as

where C1 is the concentration of ammonia in the equilibrium reaction [mol/m³], and

C2 is the concentration of carbon dioxide in the equilibrium reaction [mol/m³]

where C3, is the concentration of ammonium carbamate concentration in the reactor.

Equations (14a) and (14b) are combined to give the overall rate of ammonium carbamate in
the reactor as:

Applying equation (14c) to equation (13c) gives the rate of urea for-mation in the
reactor as follows:

Expressing equation (15) in terms of Dalton's law of partial pressure and the mole
fraction gives

Where y1 represents the mole fraction of ammonia in the equilibrium reaction, y 2 is

the mole fraction of carbon dioxide, y 3 is the mole fraction of ammonium carbamate in the

12
reaction process, and PT is the total pressure of the system [atm]. The partial pressure of the
gas is related to the mole fraction and the total pressure of the system as follows:

where Pi is the partial pressure of species i, yi is the mole fraction of species i.

(iii) The rate equation for urea formation is expressed as the extent of the reaction or
the reaction coordinates.
This is achieved by defining 1 and 2 as the reaction coordinates for equations (2a)
and (2b), illustrating the reaction's progression from reactants to products through various
intermediate and transition states, and indicating bond breaking and formation. The extent
of the reaction quantifies the progress or equilibrium state, defined as...

where dni,, is the change in the amount of i-component [mol], vi,j the stoichiometric
coefficient of the i-components in the y-coordinate and j is the extent of the reaction in the j-
coordinate [mol].
In terms of the reaction coordinates 1 and 2 the components are assigned digits as,
1(NH3), 2(CO2), 3 (carbamate), 4 (urea), and 5 (water), and the rate stoichiometrically in
terms of the extent of reaction or reaction coordinates is:

Assuming the reaction begins with n1,0 moles of NH3 and n2,0 moles of CO2, the
mathematical expressions for vi's and yi's as functions of 1 and 2 provide the mole
fractions of the various species in the equilibrium reaction process, as summarized in Table
1. Additionally, the rate of urea formation, in terms of the extent of the reaction, is given by
equation (20), respectively.

13
 (20)

2.3. Determination of rate constants and equilibrium constants

The procedure outlined below was employed to examine the rate constants and
equilibrium constants involved in the synthesis process.

(i) The equilibrium constant KC is mathematically expressed as the ratio of the forward
reaction rate constant k1 to the reverse reaction rate constant k2 for the equilibrium reaction
described in equation (2b).

(ii) The thermodynamic equilibrium constant expressed through the change in standard
Gibbs free energy G0:

The equilibrium constant KC or KP, which corresponds to species concentrations or gas

partial pressures as presented in equation (1), represents the ratio between the forward and
reverse reaction rate constants. The van’t Hoff equation provides a relationship between the
equilibrium constant and the standard Gibbs free energy, allowing for the determination of
the equilibrium constant for the reaction process using the following relation:

Equation (23) gives an expression for the equilibrium constant after manipulation (22) as,

14
where G0 is the change in Gibbs free energy [kJ/mol] and, R is the gas constant for an
ideal gas [J/mol. K] and T is the absolute temperature of the mixture [K].

(iii) The equilibrium constant can be expressed in terms of fugacity, fugacity coefficient,
partial pressure, and the extent of reaction of the involved species.
From a thermodynamic perspective, the equilibrium constant is derived using the fugacity f
and the extent of reaction . Given that the process occurs in the gas phase under elevated
pressures and temperatures, fugacity is applied as a parameter representing high-pressure
conditions in the reacting system. Accordingly, the equilibrium constant is expressed in
terms of fugacity, with units of [atm], as follows:

where f-vi,j is an operator based on the quotient of fugacity product raised to the respective
coefficients v of the j-component to the fugacity of the reactants to the exponent of
coefficient v of the i-component defined clearly as:

where fvj represents the fugacity of the products raised to the power of their
respective stoichiometric coefficients, while fvi denotes the fugacity of the reactants, also
raised to their corresponding stoichiometric values. By applying equations (24) and (25), we
obtain,

where f1 is the fugacity of ammonia, f2 is the fugacity of CO2 and f3 is the fugacity of
ammonium carbamate. Fugacity is measured in units of pressure, typically atmospheres.
The fugacity coefficient is defined as the ratio of the fugacity to the pressure of component
k, and is given by the following expression::

15
 Here, represents the fugacity coefficient, f k is the fugacity of component k, P k is the
partial pressure of component k, and k refers to components 1, 2, 3, ..., up to n, as defined
within the reaction system.

Applying equation (28) into equation (27) gives,

Substituting (17) into equation (29) and further simplification gives,

(30)

Substituting mole fractions in Table 1 into equation (30) gives,

(31)

Recognizing that in a high-pressure system the pressure drops due to the formation of
an aqueous product, the fugacity coefficient approaches unity, allowing equation (31) to be
simplified as follows:

16
 (32)

(iv) The rate constants, equilibrium constant, and extent of reaction are interconnected to
derive an expression for the reaction coordinate, also known as the extent of reaction.

The extent of reaction is determined by utilizing the relationship between the equilibrium
constant—expressed in terms of Gibbs free energy—and the procedure outlined in
algorithm "ii", through the combination of equations (22) and (32), as follows:

(33)
where 2 =21 = , P=PT is the pressure of the system [atm].
Equation (33) is solved either through the quadratic formula or by using the method of
completing the square to determine the extent of reaction. Once the extent of reaction and
the equilibrium constant are known, the rate constants can be calculated using equations
(21), (22), and (33), following the relationships provided in equations (34) and (35).

(34), (35)

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3. REACTORS

3.1. Descriptions of reactors

The urea production processes at two major fertilizer plants in Nigeria—Indorama

Eleme Fertilizer and Chemicals Limited and Notore Chemical Industries Limited—are
based on two distinct reactor technologies: Continuous Stirred Tank Reactors (CSTRs) and
Plug Flow Reactors (PFRs), respectively. Both plants are located in the Eleme Local
Government Area of Rivers State, within the Niger Delta region, and are key producers of
nitrogen-based fertilizers for both domestic and international markets.
While the overall process conditions and feed materials are largely similar between the
two facilities, a notable distinction lies in the reactor configurations employed. The
Indorama plant utilizes a series of CSTRs integrated within a Vertically Submerged
Carbamate Condenser (VSCC) for urea synthesis. This system operates at a molar
ammonia-to-carbon dioxide (N/C) ratio of 2.8–3.0, under elevated conditions of 180–182 °C
and 155 kg/cm²G pressure. The primary reactor, arranged in two stages, maintains an N/C
ratio of 3.7 with a residence time of 2.5 minutes. The design allows for minimal inert gas
usage—only one-fifth of that required in conventional CO₂ stripping processes—while
achieving a high CO₂ conversion rate of 63–64% at 182–184 °C and the same pressure of
155 kg/cm²G.
In contrast, the Notore plant employs a High-Pressure Carbonate Converter (HPCC),
functioning as a Plug Flow Reactor (PFR), where partial conversion of feedstock to urea
occurs. Liquid ammonia is delivered from the NH₃ Surge Drum via a booster pump to the
NH₃ heater, operating at 131.4 °C, before being introduced into the HPCC. The reactor
operates optimally at 183 °C, a pressure of 160 kg/cm²G, a residence time of 3.7 minutes,
and an N/C ratio of 3.3. Under these conditions, the CO₂ conversion efficiency reaches
approximately 53%.

3.2. Determination of the optimal kinetic parameters from the application of

optimization model

An optimization technique for obtaining more precise estimates of Arrhenius

constants, activation energies, and rate constants is the non-linear statistical search
regression methodology. In order to enhance urea yields in both reactors and better describe

18
the urea synthesis process, the optimization model is used to the transient reactor models
created in this work to determine the optimal kinetic parameters.

Ei(j+1) = Eij + ⍺∆
Ai(j+1) = Aij + ⍺∆
where :
Ei(j+1), Ai(j+1): the optimal activation energies and Arrhenius constants of i-components in the
equilibrium reaction process based on the convergence criterion set
Eij, Aij: are the current or input values of the activation energies and Arrhenius constants
⍺: a scalar constant ranged from 0.35 ≤ α ≤ 0.95
∆: the incremental change defined mathematically as, ∆ = -inv(JJT).J, in which inv(JJT) is
the inverse of the product of matrix J and its transpose and J is an n x p matrix.

Then, the optimized rate constant is calculated as

( j +1)
−E i
kj = Ai(j+1). exp{ }
RT

3.3. Development of the transient mole fraction and temperature models of the urea
reactors

Predicting and describing the production process within reactors under different
beginning and boundary circumstances using mathematical expressions derived from
material and energy balance principles applied to the reactors is the fundamental function of
modeling. These models' performance and error analysis determine their acceptance and
dependability.

Finding a more dependable rate expression, improving reactor performance, and

forecasting the reactor's complete process are all part of reactor modeling. Urea reactors are
taken into consideration in this analysis; the Notore reactor is modeled as a PFR, while the
Indorama reactor is modeled as a CSTR. By applying the concepts of mass and energy

19
conservation to these urea reactors, models for their mole and temperature profiles were
developed using unsteady-state material and energy balance equations.

a. Mole Fraction Models for the Reactors

The mole fraction models for the reactors were created using the general material
balance equation, which is expressed as

This equation is applied to CSTR in sequence for a single mole of reactants entering
the reactor to create urea. Using the rate expression model and expressing the urea process
in terms of mole fraction in an unstable condition:

where yi,j denotes the mole fraction of the i-component in the j-reactor (i.e., i = NH 3, CO2,
Carbamate, urea or water and j = 1, 2 or 3).

Similarly, for one mole of reactants to the reactor, the material balance equation (35)
is applied to PFR in terms of mole fraction and extent of reaction as

20
where yi denotes the mole fraction of the i-component and v is the superficial velocity [m/s].

b. Temperature Models Developed for the Urea Reactors

Similarly to the material balance model, the general energy balance equation used to
develop the temperature unsteady state models for the CSTR in series and PFR, is stated as

The temperature models below for the CSTR in series and PFR respectively, are
obtained by applying the energy balance equation above

21
where
Ti,j: the output temperature of the i-component in the j-reactor [K]
J = (-Hr)Cp [m3K]
T0: the input temperature [K]
1: the space velocity or reciprocal of space time, 1=UACpVR=v0VR
TC: the coolant temperature [K]

where
Ti,j: the output temperature [K]
J = (-Hr)Cp [m3K]
1: the space velocity or reciprocal of space time, 1=UACpVR=v0VR
TC: the coolant temperature [K]

3.4. Input parameters for simulation

The input conditions used for the simulation and validation of the models were
obtained from Indorama and Notore plants.

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 3.5. Results and discussion

a. Rate expression result

Figure … shows the concentration profiles for the various components involved in
the urea manufacturing process over time. Carbamate is created when NH3 and CO2 are
exothermically depleted (extra heat is emitted), which then endothermically dissociates to
produce urea and water. Between the starting value and 3.5 minutes, the concentration
values of NH3 and CO2 show an exponential decline from 0.5 mol/m3 and 0.4 mol/m3 to
0.20 mol/m3 and 7e-4 mol/m3, respectively. Over the same time period, the carbamate
concentration increases exponentially from 0 to 0.017 mol/m3 and then decreases
exponentially to 1.09e-5 mol/m3.

As shown in Fig. 3, these dynamics match with the lowest rate expression result for
urea synthesis, maximizing yields inside the reactors. These results are consistent with
values documented in the literature, suggesting that the rate expression model that was
constructed may be dependable for the process of producing urea from ammonia and CO2.

b. Yield of urea of the CSTR in series

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 The urea yield in the Indorama reactor, which employs a Continuous Stirred Tank
Reactor (CSTR) configuration, has been evaluated and compared with both plant data and
values reported in the literature. This yield is determined based on a mole fraction model
developed for the reactor, which incorporates a kinetic rate expression. The urea yield is
influenced by the rate of urea formation, reaching a maximum value of 0.726 at a residence
time of 2.5 minutes, corresponding to the point of lowest urea decomposition. Beyond this
point, the yield declines due to the effects of consecutive reactions. When benchmarked
against previously reported values, the modeled yield of 0.726 exceeds the literature-
reported yield of 0.60 and the initially reported plant value of 0.34, and aligns closely with
the more recent plant-reported yield of 0.64.

Profile of the yield of urea in the Indorama reactor with time

c. Yield of urea of the PFR

Similarly, the urea yield in the Notore reactor has been analyzed and compared with
both plant-reported data and literature values. The simulation of the reactor, based on a
developed rate expression model, yielded a maximum urea yield of 0.7032—significantly
higher than the Notore plant's reported value of 0.43, as well as literature values of 0.46 and

24
0.53. This elevated yield suggests that the developed kinetic model provides a reliable and
accurate prediction of the urea synthesis equilibrium. The modeling approach employed
offers a more precise representation of the process compared to existing methodologies
reported in plant operations and the literature, making it a valuable tool for both industrial
application and academic research. Although the Indorama reactor demonstrates a slightly
higher urea yield than the Notore reactor, the results are closely aligned, with a small
absolute deviation of 0.032 between the two.

Yield of urea in Notore reactor with time

d. Optimal kinetic parameters results from the optimization models

The activation energies, Arrhenius constant and rate constants constitute the kinetic
parameters that were determined, optimized and validated. The kinetic parameter values
obtained from the applications of mass action, fugacity coefficient, and thermodynamics
models were subsequently optimized using non-linear regression analysis. These results
proved instrumental in modeling and optimizing the urea reactors.

25
 The presents refined values of activation energies, Arrhenius constants, and rate
constants. Validation of these kinetic parameters with plant data resulted in error values
ranging from 0.0004 to 0.0491 for both RMSE and deviations, indicating high accuracy,
reliability, and acceptability for control, modeling, and optimization of the reactors to
enhance the description of the urea process and performance of the controller.

e. Extension: Calculation of volumes of reactors

- Plug flow reactor:

V= = 10.66

- Mixed flow reactor in series:

V= = 7.20

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