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Received 25 July 2004; received in revised form 17 November 2004; accepted 7 December 2004
Abstract
Urea is an important petrochemical product which is mainly used as fertilizer. In this study, a model is developed for the synthesis section
of an industrial urea plant. In the proposed model the urea reactor is divided into several continuously stirred tank reactors (CSTRs). It has
been considered in this study that formation of ammonium carbamate occurs through the heterogeneous reaction of carbon monoxide and
ammonia. This reaction was considered to occur only in the liquid phase in the previous works presented in the literature. The formation of
biuret in the reactor is also considered in the model which has not been considered in the previous works. The validity of the proposed model
was demonstrated using industrial data. It has been shown that there is a good agreement between the results of the model and the industrial
data. Dynamic response of the process to some important parameters in the synthesis section was also studied.
© 2004 Elsevier B.V. All rights reserved.
1385-8947/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2004.12.020
250 M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260
Table 1
Nomenclature Properties of components [4]
Component TNBP (◦ C) d (kg/m3 ) Tc (◦ C) Pc (kPa)
a moles of water added per mole of ammonium Urea 191.85 1230 431.85 9050
carbamate Ammonium carbamate 600 1100 785.27 1103.92
CA0 initial concentration of A (kmol m−3 ) Biuret 598.3 1068.9 770.52 997.31
CU0 initial concentration of urea (mol l−1 ) CO2 −78.55 825.34 30.95 7370
−33.45
density (kg m−3 )
NH3 616.07 132.4 11276.9
d H2 O 100 997.99 374.15 22120
E activation energy (kJ kg mol−1 ) O2 −182.95 1137.68 −118.38 5080.02
F molar flow rate (kg mol h−1 ) N2 −195.8 806.37 −146.96 3394.37
H enthalpy (kJ h−1 )
k rate constant of urea production (h−1 )
k rate constant of biuret production
(l mol−1 h−1 )
Kp equilibrium constant of ammonium carbamate
production (atm3 ) monia) are stripped off from the liquid phase to the gas phase.
M average molecular weight (kg kg mol−1 ) The gas flow from the scrubber which carries the stripped-
Ni number of moles of component i (kg mol) off ammonia and carbon dioxide is then introduced into the
m initial moles of carbon dioxide (kg mol) top of the carbamate condenser. Ammonia, together with the
n initial moles of ammonia (kg mol) carbamate overflow from the scrubber, is also introduced into
nt total number of moles (mol) the top of the carbamate condenser. The carbamate condenser
N/C nitrogen to carbon mass ratio is in fact a heat exchanger in which the heat generated during
P total pressure (atm) condensation of ammonia and carbon dioxide to form am-
Pc critical pressure (kPa) monium carbamate in the tube side is used to produce low
PCO2 partial pressure of carbon dioxide (atm) pressure steam in the shell side.
PNH3 partial pressure of ammonia (atm) Only part of ammonia and carbon dioxide condense in the
Qac heat produced by ammonium carbamate for- carbamate condenser and the rest react in the urea reactor in
mation (kJ h−1 ) order to supply the heat required for the urea production re-
Qb heat consumed by biuret formation (kJ h−1 ) action. Liquid and gas phases leave the carbamate condenser
Qc heat exchanging duty of condensate in carba- via two separate lines to ensure a stable flow into the reactor.
mate condenser (kJ h−1 ) Ten trays are installed in the reactor in order to improve the
Qcw heat exchanging duty of cooling water in scrub- contact between the two phases. The liquid mixture in the
ber (kJ h−1 ) reactor overflows into the stripper. The heat is supplied into
Qu heat consumed by urea formation (kJ h−1 ) the stripper by the flow of saturated steam through its shell,
Qs heat exchanging duty of steam in stripper resulting in decomposition of the remainder ammonium car-
(kJ h−1 ) bamate into urea. The gas phase exiting the reactor contains
−rA reaction rate of component A free ammonia and carbon dioxide as well as inert gas and is
(kg mol m−3 h−1 ) discharged into the scrubber.
t time (h) In the scrubber, condensation of ammonia and carbon
T temperature (K) dioxide is achieved. The heat of condensation is partly re-
Tc critical temperature (◦ C) moved in the heat exchanging part of the scrubber by cooling
TNBP normal boiling point temperature (◦ C) water. In the scrubbing part, remaining gases are scrubbed
V volume (m3 ) with the lean carbamate solution. This stream, which is a
v0 volumetric flow rate of feed (m3 h−1 ) low concentration aqueous solution of ammonium carba-
x moles of ammonium carbamate (mol) mate, is a recycle from the low pressure section of the urea
XA partial conversion of A process.
X1 partial conversion of ammonium carbamate to
urea
X2 partial conversion of urea to biuret
y moles of urea per volume that reacts at t 2. Model development
(mol l−1 )
In this section the hypothesis and necessary equations for
Subscript developing the steady state and dynamic models of the urea
I inlet synthesis section are described. A complete list of the com-
O outlet ponents involved in the process of urea synthesis as well as
their physical properties are shown in Table 1.
M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260 251
Fig. 1. Block flow diagram in the synthesis section of stamicarbon urea plant.
2.1. Hypotheses sis process occur in the liquid phase (see Section 2.3 below).
Therefore, the model is less sensitive to the choice of the
Simulation of the synthesis section of urea plant in this equation of state employed for the gas phase.
study was done based on the following assumptions: The Wilson equation was tuned for the urea synthesis
conditions. The tuning was done by changing the interac-
• Only CO2 , H2 O, NH3 and inert gases (O2 , N2 ) exist in the tion parameters such that the model prediction best fit the
gas phase. actual plant data. The complete list of temperature indepen-
• CO2 is not dissolved in the liquid phase. In fact, it could dent interaction parameters of Wilson equation are given in
only be condensed with ammonia to form ammonium car- Table 2.
bamate in the liquid phase.
• Formation of urea takes place only in liquid phase.
• Dissolution of inert gases in the liquid phase is neglected. 2.3. Reactions
• Biuret is produced only in the reactor and the stripper.
The overall reaction of urea production is as follows:
2.2. Thermodynamics 2NH3 + CO2 ⇔ NH2 CONH2 + H2 O (1)
In this study, the thermodynamic framework is based on The process of urea synthesis consists of two sequential steps.
the model developed by Isla et al. [1]. However, Wilson and In the first step, ammonium carbamate is formed by the re-
ideal gas equations [6] were employed for calculating the action between ammonia and carbon dioxide:
thermodynamic properties of liquid and gas phases, respec-
tively. A virtually identical model was presented by Agarwal 2NH3 + CO2 ⇔ NH2 CO2 NH4 (l) (2)
et al. [7] where UNIQUAC was the model of choice. It is
worth mentioning that many pairs of activity models and/or This reaction is very exothermic and fast in both directions
equations of state were examined to predict the thermody- so that it could be considered at equilibrium at the conditions
namic behavior of the gas and liquid phases in this system. found in industrial reactors where the residence time is rather
However, the closest results to the real plant data were found high. In the next step, ammonium carbamate is dehydrated to
when employing the above-mentioned pair of equations for form urea:
predicting the thermodynamic properties of the two phases.
It should be noted that the main reactions in the urea synthe- NH2 CO2 NH4 (l) ⇔ NH2 CONH2 (l) + H2 O(l) (3)
252 M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260
Table 2
Temperature independent interaction parameters of Wilson equation (cal/mol)
Component CO2 NH3 H2 O N2 H2 O2 Biuret Ammonium carbamate Urea
CO2 – −3534.00 676.20 0.00 0.00 0.00 −3782.60 −3842.70 −2100.70
NH3 69.68 – 0.00 64.23 60.23 −12.16 311.58 1272.09 234.06
H2 O −183.70 0.00 – 30.16 −6.51 −80.37 11640.70 1182.00 1862.86
N2 0.00 −31.64 7.05 – 0 0.00 −656.39 −659.98 3127.62
H2 0.00 −20.49 8.02 0.00 – 0.00 201.98 217.74 2871.87
O2 0.00 2051.30 29.19 0.00 0 – 1077.91 1082.71 3614.11
Biuret 69.68 448.00 4096.00 20.03 11.56 −12.16 – 597.00 239.00
Ammonium carbamate 69.68 1595.00 1135.00 25.00 11.56 28.00 741.00 – 171.08
Urea 69.68 650.00 1050.00 −3.00 11.56 −12.16 −55.00 197.94 –
2NH2 CONH2 ⇔ NH2 CONHCONH2 + NH3 (5) The formation of urea and biuret are considered as slow
reactions and far from the equilibrium in the urea reactor. For
This reaction is slow and endothermic. Biuret formation takes the urea formation reaction (reaction (3)), the rate equation of
place when there is a high urea concentration, low ammonia Claudel et al. [13] in the presence of initial water have been
concentration and high temperature [8,9]. employed:
Three main reactions considered in the process are forma-
dX1
tion of ammonium carbamate (4), formation of urea (3) and = k(1 − X1 )(a + X1 ) (7)
formation of biuret (5). The residence time in the urea reactor dt
is high enough in order the reaction of ammonium carbamate In the case of biuret formation reaction, the rate equation
formation to be practically considered at equilibrium in the proposed by Shen [14] was employed:
effluent [10]. Therefore, in order to calculate the conversion dy
of carbon dioxide in the urea reactor the equilibrium constant = k (CU0 − y)2 (8)
dt
of reaction (4) should be known. The equilibrium constant of
this reaction has been already investigated [10–12]. In the The kinetic parameters of Eqs. (7) and (8) are given in Table 3.
present study, the temperature dependent formula of Egan et
al. [11] has been adopted due to the fact that it covers a wide 2.4. Process equipments
range of temperature. Moreover, in order to further enhance
the accuracy of the model, in addition to the data reported 2.4.1. Carbamate condenser
by Egan et al. [11], existing equilibrium data at the indus- The equations related to the dynamic behavior of the car-
trial urea reactor outlet was also taken into account and the bamate condenser are summarized in Table 4. Carbamate
equilibrium constant was improved as follows:
Table 3
7.6569 × 103 Kinetic parameters
log Kp = − + 22.161 (6)
T k0 E (kJ/kg mol)
k [13] 1.9 × 105 4.2 × 104
The data reported by Egan et al. [11] as well as the plant data k [14] 2.1 × 107 8.5 × 104
and are shown in Fig. 2.
Table 4
Model equations
Section Equation Description
d(VCarbamate−Condenser d)
Carbamate dt = F I M I − FO M O Overall mass balance
condenser d FO,CO2
FI,CO2 − FO,CO2 − rCO2 VCarbamate−Condenser = VCarbamate−Condenser dtd M FO Mole balance for carbon dioxide
d FO,Carbamate
253
254 M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260
Table 5
Typical industrial feed conditions of an urea production plant
Feed P (kg/cm2 ) T (◦ C) Carbon dioxide Ammonia Water Nitrogen Oxygen Urea Ammonium
(mol%) (mol%) (mol%) (mol%) (mol%) (mol%) carbamate (mol%)
CO2 146 130 89.0 0 4.5 4.6 1.9 0 0
NH3 146 40.5 0 99.0 1.0 0 0 0 0
Lean ammonium carbamate 143 73.0 0 14.5 59.9 0 0 0.1 25.5
256 M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260
Fig. 6. Parity plot of urea wt.% in the outlet of urea reactor and stripper at
Fig. 5. Comparison between model temperature distribution and industrial capacities of: 95%, 106%, 109% and 113%.
distribution of temperature along the reactor.
predictions of weight percent of urea in the liquid outlet of
actor is: the urea reactor and the stripper against plant data at different
plant capacities are also shown in Fig. 6 which again illus-
HI − HO + Qac − Qu − Qb = 0 (14) trates that the model satisfactorily meet the plant data.
If Eq. (14) is not satisfied, the assumed temperature of
the reactor outlet was changed accordingly and the above- 3.1. Case studies
mentioned calculations were repeated from the beginning.
The iterative procedure was repeated until the energy bal- Effect of changes in some key parameters on the behavior
ance equation is satisfied from which the exit temperature of the synthesis section was investigated based on the model
and composition of each CSTR were established. developed in this work. Some of these case studies are given
The validity of the proposed model was tested against the below.
steady state data obtained at industrial scale. Fig. 5 illustrates
the comparison between the model prediction and plant data 3.1.1. Pressure of the shell of carbamate condenser
in terms of the temperature profile along the urea reactor. It The heat exchanged between shell and tube influences the
could be seen in this figure that the model predicts the actual amount of carbon dioxide converted to ammonium carba-
temperature inside the urea reactor satisfactorily. mate. In a real plant, the amount of gas entered to the urea
Moreover, calculated results and the plant data on some reactor is controled by the pressure of saturated stream in the
key operating parameters of the urea synthesis section are shell side of the carbamate condenser. Higher steam pressure
given in Table 6. Comparing the simulated values with the corresponds to smaller temperature difference between the
plant data in this table also confirms that the model predic- cooling and process sides, i.e., lower heat flux.
tions are in good agreement with the plant data. The model Effect of increasing the pressure of the shell of carbamate
condenser on the conversion of CO2 to urea and biuret as
Table 6 well as the concentration of biuret in the liquid outlet flow of
Comparison between plant data and simulation results the urea reactor are shown in Figs. 7 and 8. As it is shown
Parameter Unit Plant data Simulation in these figures there exists a local maximum in all these
Inlet temperature of urea ◦C 169.3 169.5 curves. Since increasing the pressure in the shell of the car-
reactor bamate condenser results in increasing its temperature, it is
◦C
Outlet temperature of 183 182.5 necessary to investigate the effect of the temperature on the
urea reactor conversion of the two main reactions occurring in the urea re-
Urea concentration at urea wt.% 33.9 33.0
reactor liquid outlet
actor, i.e., ammonium carbamate and urea formation. Effect
N/C ratio at urea reactor – 2.9 3.1 of temperature on the equilibrium conversion of ammonium
outlet carbamate formation and urea formation are shown in Fig. 9.
◦C
Inlet gas temperature of 186.9 186.1 Since formation of ammonium carbamate is an exothermic
carbamate condenser reaction (reaction (4)), increasing the temperature beyond
◦C
170 ◦ C causes decreasing the formation of ammonium car-
Outlet gas temperature of 114.6 116.4
scrubber
bamate, as seen in Fig. 9. On the other hand, it is shown in
M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260 257
Fig. 10. Effect of liquid level in the carbamate condenser drums on the
conversion of CO2 to carbamate in the tube side of carbamate condenser and
on the conversion of CO2 to urea in the reactor.
Fig. 12. Effect of liquid level in the drums of carbamate condenser (a) on
the flow rate of exit gas (b) on the conversion of CO2 to urea in the liquid
outlet of the reactor (c) on the conversion of CO2 to biuret in the liquid outlet
Fig. 11. Effect of liquid level in the carbamate condenser drums on the
of the reactor.
conversion of CO2 to biuret in the reactor.
M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260 259
4. Conclusions
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[7] R.K. Agarwal, Y.-K. Li, O.J. Santollani, M.A. Satyro, Modeling of [12] D. Janjic, Etude de I’equilibre de dissociation du carbamate
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from urea, Ind. Eng. Chem. 50 (1958) 633–636. kinetics investigation of ammonium carbamate decomposition into
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