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Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.

com, ISSN 1743-3533

Simulation of urea reactor of industrial process


X.P. Zhang, P.J. Yao, D. Wu & Y . Yuan
Institute of Process Systems Engineering,
School of Chemical Engineering,
DaZian University of Technology, China

Abstract
The urea reactor is one of the most important units in the urea synthesis process.
Rigorous simulation of the urea reactor is necessary and significant. Ho,wever, the
complicated thermodynamic system and chemical reactions result in difficulties
of modeling and simulation. In this work, the urea reactor is considered as a
critical gas-liquid concurrent fluid reactor, in which some perforated plates are
installed in order to prevent back mixing. A mechanism model is presented based
on a rigorous thermodynamic model, reaction kinetics and fluid dynamics. A
stage-by-stage method is adopted to solve the urea reactor model that consists of
a series of non-linear equations. The numerical solution of the equations is
substantially performed with a conventional iterative method and the algorithm is
simple and robust. The solution gives the profile of the temperature along and the
concentrations of components within the reactor. The model results agree well
with design data.

1 Introduction

In urea synthesis process, the conversion of carbon dioxide into urea determines
the material consumption. In order to improve the conversion of COz, many urea
companies have improved the structure of urea reactor, for example, some
perforated plates have been introduced into urea reactor with the aim of reduced
the back-mixing. Recently, high efficient plates designed by Snam, Starnicarbon,
TOYO, Casalo, etc. have been applied commercially to the plants. As a result,
while the flow entering at the bottom and generating an upward movement, the
reactor approaches the behavior of tubular, plug flow reactor without
concentration back mixing. In the other hand, high efficient plates make the
sufficient contact between liquid and vapor on the plate, which enhance the heat
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

66 Computational Methods in Mlrltiphas~F l o ~ ,

and mass transfer process. Combined with the study [l] and applications in the
urea plants [2], it is clearly that the behavior of the reactor are dominated by both
the kinetics of urea formation and the heat and mass transfer between the phases.
Based on the thermodynamics of vapor-liquid phase equilibrium, chemical
reaction kinetics and the fluid dynamics, the mathematical model of urea reactor
is established and the numerical solution of the equations is performed through
conventional methods.
M. Dente et al. [l] developed a robust and suitable simulation model
considering thermodynamics, kinetics and fluid dynamics. However, the vapor-
liquid equilibrium model of NH3-CO,-H,O-urea system that played a very
important role in simulation process was presented by a semi-experimental
approach, in which the parameters were evaluated by regression of experimental
data. Irazoqui and Isla [3] simulated the isothermal urea reactor composed of
internal coil and main reactor. With the extended UNIQUA equation, mechanism
model of NH3-CO,-H,O-urea system was used [4]. Wei [5] introduced
equilibrium stage model into Stamicarbon urea reactor. This model indicated that
in each plate the reactor is assimilated to a CSTR with perfect mixing and the
outlet vapor and liquid could reach vapor-liquid phase equilibrium and chemical
reaction equilibrium. This model is simple and easy to be resolved.

2 Thermodynamic framework

A robust, rigorous and available thermodynamic model is critical in chemical


process simulation. In the urea reactor, the vapor-liquid equilibrium (VLE) of
NH3-CO2-H20-ureasystem should be considered in the synthesis conditions
(According to the different techniques, pressure ranges from 13 to 25 MPa,
temperature ranges from 180 to 220%). Because of the chemical reactions and
electrolysis reactions, the liquid phase consists of ions and molecular, e.g. NH,' ,
HCO; , NH, etc. In order to simulate this thermodynamic system, activity
coefficients can be estimated by equation of state (EOS) or activity coefficient
method. In tlus electrolyte system, its behavior has been extensively studied
under conditions removed from those at which urea is formed [6] and under urea
synthesis conditions [1][4][7]. It is evidence that it is hard to find one
thermodynamic model to satisfy the experimental data in all range of
concentrations, temperature and pressure. For example, Edwards's model is only
suitable for the dilute weak electrolyte [6], whereas Isla model yields good
agreement under the conditions of urea synthesis [4]. With the aim of simulating
urea reactor, extended UNIQUAC equation is selected to resolve the VLE of
NH,-CO2-H,O-urea system. Vapor fugacity coefficients of vapor components are
predicted by Nakamura al. [S].
Under urea synthesis conditions, the following reactions occur:
C 0 , ( 1 ) + 2 N H 3 ( 1 ) = H , N C O O S + NH,' ( 1
C 0 , ( 1 ) + N H , ( I ) + H , 0 ( 1 ) = H C O 3 . + NH,' ( 11
C0,(1) + NH,(l) = H,NCOOH(l) ( 111
H 2 N C O O - + NH,' = H , N C O N H , ( l ) + H , 0 ( 1 ) (W >
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

Computational Methods in Multiphase Flow 67

Compared with the fast and strong exothermic reaction 111, urea
formation reaction IV is slow and endothermic. Reaction I , I1 and I11 are so
fast, in both the directions, that can be practically considered at the equilibrium.
The reaction IV constitutes the rate determining step for urea formation. As a
result, in liquid phase, the true species are as follows: H,O (l), NH, (2), CO, (3),
NH,'(4), HCO,' (5), H,NCOO' (6), H,NCOOH (7), H,NCONH, (8); and in
vapor phase, are H,O (l), NH, (2), CO, (3).
In the total process of urea synthesis, because of the reaction residual time
and reaction conditions (such as temperature and pressure), except for the urea
reactor, reaction in the other units, e.g. high pressure condenser, C02 stripper,
high pressure scrubber, the reaction IV can be ignored. 'The amount of urea
formation will be calculated through kinetic equation of reaction IV.
Extended UNIQUAC equation is used by Bernadis et al. [7] to estimate the
activity coefficients in the W,-CO,-H,O-urea system. In the activity coefficient
equations, Dybye-Hiickel contribution that depends on temperature, ionic species
and ionic strength is introduced into the UNIQUAC equation. Isla et al.
reestimated [4] almost all the parameters and made this thermodynamic model
yield good agreement with experimental data.
About phase equilibrium, based on the dissolved properties of spacies,
different relationships are used for those components. For H,O and CO,,
considered Lewis-Randall fugacity rule as standard state, then the phase
equilibrium equations are as fellows:
Standard fugacities f,' are defined under the system tempemture and zero
pressure, then equations can be expressed:

i=H,O, NI-I, (1)


For CO,, Henry's law is adopted for standard state, then vapor-liquid
equilibrium equation is:

Combined chemical reaction I ,11,111 and IV,VLE relationships (l), (2)


as well as activity coefficients equations, the thermodynamic model of NH,-CO,-
H,O-urea system can be solved. In this paper, we reestimated some parameters in
eqn (1) so as to make the model yield good agreement with the designed
production-scale data.

3 Rate of the urea formation reaction

The kinetics equation of urea formation reaction IV is as follows:

Reaction rate constant k:


1 xr, xr,
xr4 l
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

4 Fluid dynamic model

4.1 Reactor fluid dynamic analysis

As pointed out before, vapor-liquid two-phase flow enters at the bottom and
discharges from the top. Along the reactor, the pressure, temperature and
concentrations of components in vapor and liquid are changed.
In each perforated plate, the vapor mixture moves through swarms of
bubbles, generated by the holes of the sieve tray, and the bubble swarms are
intermittent: Meanwhile, heat and mass transfer between the phases. This
concurrent process can be described as follows:
First, CO, and W, enter into liquid through gas films. Then, CO, and NH,
in liquid phase are combined to form carbarnate and this reaction can reach
chemical equilibrium at once. After that, the reaction IV occurs and the urea is
formed.
At the bottom of he reactor, the two-phase flow enters into the reactor.
Along the reactor, the liquid is increasing at the expense of the vapor phase,
NH,,CO,,H,O, urea (and the ions related to them ) change their relative amount
and are exchanged between the two phases; urea resides into the liquid. The
chemical equilibrium of reaction I , I1 and 111, the kinetic of reaction IV as well
as mass and heat transfer between phases dominated the behavior of the reactor.
In order to simply the simulation of urea reactor, the modeling of reactor is
based on the following assumptions (for each plate):
The liquid phase is completely mixed and the vapor phase is a plug-flow.
Two-film theory is used for the mass transfer process. Component i in
vapor and liquid phase reaches phase equilibrium in the interface.
Reaction I , I1 and 111 are fast and can reach chemical equilibrium in each
plate. The amount of urea is donunated by the kinetics of reaction N .
Urea is considered only in the liquid phase, inerts are in the vapor phase.
Heat transfer resistance between phases is ignored, which means that the
temperatures of vapor phase and liquid phase are set equal.

4.2 Mass transfer equation

Mass transfer flux of component i through vapor film:


NG = kG . (y, - y f )
Mass transfer flux of component i through liquid film:
NI = kf . (X,[- x i )
In the phase interface, component i reaches phase equilibrium:
y iI = M i ' X iI
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

In eqn (6), the equilibrium constants 'hi" are not common ones that
appear in nonelectrolyte aqueous. Here, they just can be regarded as "pseudo-
equilibrium constants" whch depend on temperature, pressure, and chemical
reaction equilibrium constants. With the thermodynamic model discussed
above, "mi" of component i in NH,-CO,-H,O-urea system can be calculated
under the urea synthesis conditions.
The flux of component i through vapor film and liquid film is equal:
N; = N~~ (7)
Combined eqns (4), (S), (6) and (7) to eliminated the interface mole
l
fraction X and y' , then:
N, =K:+, -
where
1
- - --
1 +L
m.
K; k; kk
From eqns (4) to (9), we can see that the mass transfer equations look
same in style with those without chemical reactions, but the equilibrium
constants "mi" have different physical meaning, just as illustrated above.
Considering tlus special system, the rates of reaction I , I1 and 111 are too
high that they can complete in the liquid film. As a result, the mass transfer rate
of component i is greater than that in vapor film, i.e. k; >> k: , then eqn (9)
can be expressed: K = kp .

5 Simulation of urea reactor

5.1 Reactor model

The plate conceived is schematically shown in figure 1.

plate

Figure 1: Sketch map of one plate

Based on the VLE, fluid dynamic equation and mass transfer equations,
the reactor model is proposed. For each plate, the involved equations are as
follows:
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

70 Computational Methods in Multiphase Flow

Mass transfer equations:


N, = kG -m,. x i ) (10)
Vapor phase (plug-flow) mass balance (for component i)
dG,=Ni.a.dVR (11)
Liquid phase (completely mixed) mass balance (for component i)
AL,, = I ~ G+ v, i .Rev, (12)
Total heat balance in each plate
Lout H:,,a + Gout. H:,, = Lin . H: + Gin H:
(13) + Q,
Resolving above non-linear equations composed with eqns (l), (2), (3),
(10), (ll), (12) and (13), the profiles of temperature, concentrations both in
vapor and in liquid can be obtained.

5.2 Mass transfer coefficients and effective interface area

Mass transfer coefficients and effective interface area are the critical parameters
in the simulation process; their accuracy will determine the result of the
simulation. In general, we can obtain these parameters by experiments.
However, while lacking of experiment data, dimensionless formulas are often
used to derive the mass transfer coefficients. In order to agree well with plant
data, the conditions under which we study should approach the conditions that
the dimensionless formula is available. Even though, in many circumstances,
the formulas should be rectified. The following dimensionless formula is used
here to evaluate vapor mass transfer coefficients ko [l].

Where

The properties of diffusion coefficient, viscosity, surface tension and


density are derived from handbook [9].
In formulas (14), 15, bubble diameter Db is calculated as follows [l]:

Where
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

Computational Methods in Multiphase Flow 71

Then, effective interface area:


5 . ~
a=-
Db
5.3 Simulation of the reactor model

As pointed above, according to the assumptions on the reactor model, liquid is


treated as the completely mixed flow, the temperature and components on each
plate are the same; vapor flow belongs to the plug-flow, the components along
the reactor are different. While solving this non-linear equation set, the
components profile in each plate should be assumed at first. Using two- layer
iterative method, mass balance and mass transfer equations are solved inside
layer, and outlet temperature in each plate can be calculated outside layer. The
average total pressure in each plate is defined as the reactor bottom pressure
reduced of the average hydrostatic pressure corresponding to the plate.

6 Result of simulation and discussion


The result of simulation is shown in table 1.

Table 1 Temperature, Flowrate, and concentrations along reactor

Compared the results of model and the designed data of commercial plant,
the temperature and components of outlet streams are in good agreement,
which is shown in table 2. It means that proposed model is available and
reliable.
Table 2: Comparison of this model with designed data [l01
Outlet T
*C
NH, CO2
Liauid
H20
mole fraction

Urea
I
NH,
Vaaor
CO2 H20
1
J

This work 183.8 0.4610 0.1254 0.2671 0.1517 0.6342 0.2338 0.0429
~ e s i ~ n edata'
d 183.0 0.4635 0.1176 0.2679 0.1509 0.6709 0.2121 0.0363
Relative error % 0.437 0.539 6.633 0.2986 0.5301 5.470 10.23 18.20
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

The temperature profile along the reactor is shown in figure 2. Because


the reaction I is fast and exothermic and the reaction IV is slow and
endothermic, in the beginning, the temperature of this system rise quickly,
then high temperature can increase the rate of reaction Nand make it
move to the forward direction, thus much more urea is formed. Both of
the two functions result in that the temperature along the reactor rises at
first, then attends to a highest point and decreases gradually. The shape of
temperature profile shown in figure 2 is difficult to measure in plant-scale
operation but really very important in operating, reforming and optimizing
the urea reactor,

0 1 2 0 4 5 6 7 8 9
P l a t e No.

Figure 2: Temperature profile along the urea reactor

7 Conclusion
In this paper, the model of urea reactor is proposed based on thermodynamic
VLE of NH,-CO2-H,O-urea system, chemical reaction kinetic and fluid
dynamics and the numerical solution of the equations is performed through
conventional methods. The result agrees well with designed data. The
temperature profile, which is difficult in measuring in practice, is obtained. It
will be significant in operating, reforming and optimizing the urea reactor.

Nomenclature

a : active interfacial area, m2/m3


C, : total concentration of the vapor phase, mol/m3
HmG,H,~, H,,,?, H,: :enthalpy of vapor and liquid
k,: k: Ki, : mass transfer coefficients, kmoVm2 s
Kxr,4 : equilibrium constant of reaction IV
L, G : liquid and vapor flowrates, kmoVhr
mi : pseudo-equilibrium constant
Niq N t : total vapor and liquid mass fluxes, kmoVhr
R4 : rate of reaction N , kmol/m3 hr
VG,VL : velocities of vapor and liquid flow, m/s
Transactions on Engineering Sciences vol 30, © 2001 WIT Press, www.witpress.com, ISSN 1743-3533

VK : volume of reactor, m'


XI : molar fraction of conlponent i , i= H,O, NH,, CO,, urea
%l ,Y,' : interfacial molar fraction of i , i= H,O, NH,,CO,
Xr, : molar fraction of real species in liquid phase
t : vapor hold-up
o : surface tension, N/m
P : density, kg/m3
d, : fugacity coefficient of component i
YI : activity coefficient of conlponent i
v, : stoichiometric coefficient

References

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[2] Wan Y., Application of h g h efficient urea converter trays. Da Dun Fen, 2 1(3),
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[3] Irazoqui H. A. & Isla M. A. Simulation of Urea Synthesis Reactor. 2. Reactor
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[4] Isla, M. A., Irazoqui, H. A. & Genoud, C.M. Simulation of Urea Synthesis
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[7] Bernadis M. & Carvdi G. Urea-NH,-CO2-H20: VLE caculations using an
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[S] Nakanura, R C., Bread Veld, J F. & Prausnitz, J M. Thermodynamic
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[9] Perry Jolul H., Perry S Chemical Engineering Handbook, McGraw-HILL
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