Professional Documents
Culture Documents
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
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 vaporliquid 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
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:
xr, xr,
xr4
IV
is as follows:
Transactions on Engineering Sciences vol 30, 2001 WIT Press, www.witpress.com, ISSN 1743-3533
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
NG = kG . (y, - y f )
Mass transfer flux of component i through liquid film:
NI = kf . (X,[- x i )
Transactions on Engineering Sciences vol 30, 2001 WIT Press, www.witpress.com, ISSN 1743-3533
N, =K:+,
where
1
1
- - --
K;
k;
m.
+L
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 .
plate
Transactions on Engineering Sciences vol 30, 2001 WIT Press, www.witpress.com, ISSN 1743-3533
70
N, = kG
-m,. x i )
(10)
dG,=Ni.a.dVR
(11)
AL,, =
I ~ G+ v, i .Rev,
(12)
Lout H:,,
+ Gout. H:,,
= Lin . H:
+ Gin
H:
+ Q,
(13)
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.
a
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
Where
Transactions on Engineering Sciences vol 30, 2001 WIT Press, www.witpress.com, ISSN 1743-3533
71
a=-
5 . ~
Db
5.3 Simulation of the reactor model
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
This work
~ e s i ~ n edata'
d
Relative error %
183.8
183.0
0.437
NH,
0.4610
0.4635
0.539
mole fraction
Liauid
I
Urea
H20
CO2
NH,
0.1254 0.2671 0.1517 0.6342
0.1176 0.2679 0.1509 0.6709
6.633
0.2986 0.5301
5.470
Vaaor
CO2
0.2338
0.2121
10.23
1
J
H20
0.0429
0.0363
18.20
Transactions on Engineering Sciences vol 30, 2001 WIT Press, www.witpress.com, ISSN 1743-3533
P l a t e No.
Conclusion
Nomenclature
a
C,
R4
VG,VL
m2/m3
mol/m3
:enthalpy of vapor and liquid
: mass transfer coefficients, kmoVm2 s
: equilibrium constant of reaction IV
: liquid and vapor flowrates, kmoVhr
: pseudo-equilibrium constant
: total vapor and liquid mass fluxes, kmoVhr
: rate of reaction N , kmol/m3 hr
: velocities of vapor and liquid flow, m/s
Transactions on Engineering Sciences vol 30, 2001 WIT Press, www.witpress.com, ISSN 1743-3533
VK
XI
%l
,Y,'
Xr,
t
o
P
d,
YI
v,
References
[l] Dente M,, Rovaglio M., Bozzano G. & Sogaro A. Gas-liquid Reactor in the
Synthesis of Urea, Chemical Engineering Science, 47(9-1 l ) , pp. 2475-2480,
1992.
[2] Wan Y., Application of h g h efficient urea converter trays. Da Dun Fen, 2 1(3),
pp. 154-157, 1998.
[3] Irazoqui H. A. & Isla M. A. Simulation of Urea Synthesis Reactor. 2. Reactor
Model. IECR, 323(l l), pp. 267 1-2680, 1993.
[4] Isla, M. A., Irazoqui, H. A. & Genoud, C.M. Simulation of Urea Synthesis
Reactor. 1. Tllernlodynamic Framework. IECR, 323(1 l), pp. 2662-2670,
1993.
[5] Wei S.A., Research and development of the simulation system of the ureasynthesis process, Doctoral paper, Dalian University of Technology, China.
[6] Edwards T. J., Newman J. & Prausnitz J. M. Vapor-Liquid Equilibrium in
Multiconlponent Aqueous Solutions of Volatile Electrolyte, AIChE J., 24(6),
pp. 966-976, 1978.
[7] Bernadis M. & Carvdi G. Urea-NH,-CO2-H20: VLE caculations using an
extended UNIQUAC equation. Fluid Phase Equilbria, 53, pp. 207-218,
1989.
[S] Nakanura, R C., Bread Veld, J F. & Prausnitz, J M. Thermodynamic
Representation of Gas Mixtures Containing Common Polar and Nonpolar
components, IEC PDD, 15, pp. 557-564,1975.
[9] Perry Jolul H., Perry S Chemical Engineering Handbook, McGraw-HILL
BOOK COMPANY,INC. New York Toronto London, 1963
[l01 Yuan Y. & Wang W. S. Fertilizer engineering series: urea. Chemical
engineering publishing company, Beijing, China, 1997.