Zhang Elsevier
Zhang Elsevier
Zhang Elsevier
Received 28 October 2003; received in revised form 14 July 2004; accepted 11 October 2004
Available online 6 January 2005
Abstract
In this paper, modeling and simulation of high-pressure urea synthesis loop has been studied. The extended electrolytic UNIQUAC equation
has been used to describe the nonideality of liquid phase of NH3 –CO2 –H2 O–urea system under high pressure and high temperature, and the
perturbed-hard-sphere (PHS) equation of state has been used to predict the vapor fugacity coefficients. The vapor–liquid equilibrium has been
treated simultaneously with chemical reactions due to the complex features of the urea synthesis system. A concrete procedure for simulation
of the key units and flowsheet of the high-pressure urea synthesis loop has been developed. The equilibrium-stage model has been applied to
modeling and simulation of the urea reactor, CO2 stripper and other key units in the high-pressure loop for urea synthesis, and the simultaneous-
modular approach has been adopted to simulate the flowsheet. The simulation results have been found to be in good agreement with the design
data from the industry-scale plant. This work provides an effective tool and significant guidance for design or retrofit of urea synthesis process.
© 2004 Elsevier Ltd. All rights reserved.
PACS: 07.05.T
Keywords: Simulation; Phase equilibrium; Urea synthesis process; NH3 –CO2 –H2 O–urea system; Simultaneous-modular approach
0098-1354/$ – see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2004.10.004
984 X. Zhang et al. / Computers and Chemical Engineering 29 (2005) 983–992
was used to describe liquid activity coefficients of molecular where fi0 is defined as standard fugacity under the system
and ionic species in NH3 –CO2 –H2 O–urea system in terms temperature and zero pressure.
of Sander and Isla’s work, and vapor fugacity coefficients For CO2 , Henry’s law was applicable, and vapor–liquid
were represented by perturbed-hard-sphere (PHS) equation equilibrium equation was represented as Eq. (7), and HCO2
of state proposed by Nakamura, Bread, and Prausnitz (1975). is the Henry coefficient of CO2 .
The extended UNIQUAC equation consists of three items
as the follows (Sander et al., 1986, 1986a, 1986b; Isla et al., υiL (P − P1s )
pyΦi = γi xi HCO2 exp (7)
1993): RT
ln γ (T, X) = ln γ C (T ) + ln γ R (T, x) + ln γ D–H (T, X)
i i i i (1)
The vapor fugacity coefficient Φi was estimated with the
where the combinatorial ln γi
and the residual ln γiR contri-
C
PHS equation of Nakamura et al. (1975). All the parameters
butions to the activity coefficients are given by including binary interaction parameters, chemical equilib-
rium constants, Henry’s constants and standard fugacity of
φi z θi φi
ln γi = ln
C
+ qi ln + li − xj lj pure component were obtained by fitting against the experi-
xi 2 φi xi
j (2) mental data (Zhang, Chen, Liu, Yao, & Yuan, 2001a; Zhang,
Yao, Wu, & Yuan, 2001b).
Table 1 shows the model sensitivity to changes in the im-
θj τij portant variables: temperature, NH3 /CO2 and H2 O/CO2 in
ln γiR (T, X)= − qi ln θj τji −1+ the region of HP urea synthesis loop. It can be noticed that the
k θk τkj
j j thermodynamic model could satisfy the requirement of indus-
(3) trial calculation considering the average relative deviations
for equilibrium conversion rate of CO2 and total pressure
a being 1.75 and 7.89%, respectively. Figs. 1 and 2 show the
qi xi ri xi ji
θi = , φi = , τji = exp − thermodynamic character of liquid–vapor-phase equilibrium
j qj xj j rj x j RT in conditions of industrial urea synthesis process. The pa-
rameter a refers to the NH3 /CO2 (mol), b refers to H2 O/CO2
Z (mol), P refers to the equilibrium pressure and xCO2 refers to
li = (ri − qi ) − (ri − 1)
2 the equilibrium conversion rate of CO2 .
Table 1
Comparison between the experimental data (Mei, 1994) and the calculated results
Temperature (◦ C) NH3 /CO2 and H2 O/CO2 Equilibrium conversion Equilibrium pressure
(mol) in liquid phase rate CO2 (%) (MPa)
NH3 /CO2 H2 O/CO2 Cal. Exp. Cal. Exp.
161.5 4.03 1.03 64.75 68.8 7.83 9.22
171.5 3.89 0.85 66.72 64.9 8.929 9.907
171.5 4.49 0.75 71.49 69.8 9.98 10.985
176.5 4.01 0.09 78.77 78.6 10.455 11.868
176.5 4.23 0.92 68.08 67.3 9.4 10.091
186.5 4.00 0.06 79.27 79.2 16.1 14.514
186.5 4.24 0.89 68.67 68.4 15.1 13.239
196.5 3.93 0.07 78.57 79.5 17.79 18.046
196.5 4.03 0.30 75.49 76.8 17.77 17.948
Fig. 2. Dependences of equilibrium pressure and conversion of CO2 on temperature and a at b = 0.46.
X. Zhang et al. / Computers and Chemical Engineering 29 (2005) 983–992 987
Table 2
Comparison of simulation results with design data (Yuan & Wang, 1997)
Outlet stream Temp (K) Liquid mole fraction Vapor mole fraction
NH3 CO2 H2 O Urea NH3 CO2
Cal. 455.9 0.4645 0.1051 0.2792 0.1512 0.6280 0.2429
Design 453.1 0.4635 0.1176 0.2679 0.1509 0.6709 0.2121
Relative deviation (%) 0.164 0.216 10.63 4.22 0.199 6.39 14.5
Table 3
Comparison of simulation results of stripper with design data (Yuan & Wang, 1997)
Heat duty (GJ h−1 ) 139.5
Theoretical stage number 12
Urea hydrolyze rate (%) 4
Fig. 12. Profiles of flow rate in liquid phase along the stripper.
Fig. 10. Temperature profile along the reactor.
matrices Pi (i = 1, . . ., 21) can be produced. Repeating this tion reaction is strongly exothermic and so fast that can be
procedure until all the matrices are convergent. Because of ap- practically considered at the equilibrium, and the carbamate
plying the simultaneous-modular approach, the convergence dehydration reaction giving urea and water is endothermic,
of procedure is good and the computing time is short. This slower than the first one and does not proceed to completion.
approach can avoid resolving very large nonlinear equations In general, the urea synthesis reaction is exothermic and rate-
and partitioning and tearing the recycle streams. based by the dehydration reaction, so the profile of tempera-
With this developed program, the HP urea synthesis loop ture is increasing along the reactor from the feed stage to the
of CO2 stripping technology was simulated. Simulation re- outlet stage. And also, the flow rates of urea and water are
sults of key streams are compared against plant design data increasing at the expense of reactants ammonia and carbon
in Table 4, showing a very good agreement between calcu- dioxide.
lated and measured outlet streams values, temperature and The profiles of component flow rates in liquid phase along
pressure, which indicates that the developed procedure can the CO2 stripper are shown in Fig. 12. With feeding the strip-
be applied in the industrial process and it also demonstrates ping reagent CO2 , NH3 and CO2 in liquid phase will be
that the algorithm is stable and reliable. stripped gradually into the vapor in high temperature, the
Some important profiles of the critical units are also ob- result is along the stripper, the flow rates of NH3 and CO2
tained from the developed procedure. The profile of tempera- are decreasing while urea and water is holding the line basi-
ture along the urea reactor is shown in Fig. 10, and the profiles cally. Fig. 13 shows the profile of CO2 concentration along
of component flow rates are shown in Fig. 11. In urea reac- the stripper and indicates that the total stripping process could
tor, two independent reactions contribute significantly to the be divided into three phases: in the first phase, a small quan-
urea synthesis process: the carbamate formation reaction and tity of CO2 in the vapor phase will be absorbed and the CO2
the carbamate dehydration reaction. The carbamate forma- mole fraction in liquid phase will increase slightly, i.e. so-
Fig. 11. Profiles of flow rate in liquid phase along the reactor. Fig. 13. Profile of CO2 concentration in liquid phase along the stripper.
X. Zhang et al. / Computers and Chemical Engineering 29 (2005) 983–992 991
Table 4
Comparison of simulation result of HP loop with design data (Yuan and Wang, 1997Yuan & Wang, 1997)
Stream code Stream connect Flow rate of component (kmol h−1 ) Pressure (MPa) Temp. (◦ C)
H2 O NH3 CO2 Urea
S2 From unit 3a to unit 1a Cal. 82.0 1616.4 556.2 0.0 14.3 167
Design 84.5 1620.1 540.0 0.0 14.1 167
Relative deviation (%) 2.93 0.22 3.0
S5 From unit 3 to unit 1 Cal. 954.3 5359.4 1880.3 1.95 14.3 167
Design 951.9 5581.2 1962.5 1.96 14.1 167
Relative deviation (%) 0.25 3.97 4.19 0.51
S3 From unit 1 to unit 4 Cal. 35.90 616.0 235.0 0.0 13.9 182
Design 36.9 682.7 215.9 0.0 13.8 183
Relative deviation (%) 2.71 9.76 8.84
S7 From unit 1 to unit 2 Cal. 2389.7 3754.3 876.2 1292.8 13.9 182
Design 2283.6 3950.4 1002.5 1286.3 14.1 183
Relative deviation (%) 4.64 4.96 12.6 0.51
S1 From unit 2 to unit 3 Cal. 214.7 3260.7 1858.3 0.0 13.5 181.6
Design 206.2 3435.9 1955.2 0.0 14.1 180
Relative deviation (%) 4.14 5.10 4.96
S8 From unit 2 to LP loop Cal. 2116.6 597.5 297.1 1219.6 13.0
Design 2025.9 617.3 308.7 1234.7 14.1 168
Relative deviation (%) 4.48 3.2 3.76 1.22
S6 From unit 4 to unit 5 Cal. 821.5 1337.3 578.3 1.95 14.0 165.5
Design 830.1 1387.58 547.4 1.96 13.8 165
Relative deviation (%) 1.04 3.63 5.64 0.51
S4 From unit 4 to venting Cal. 0.11 1.48 0.08 0.0 14.1 90
Design 0.0 1.71 0.0 0.0 13.8 100
a Unit code: 1, reactor; 2, stripper; 3, condenser; 4, scrubber; 5, ejector.
Bernardis, M., Carvoli, G., & Santini, M. (1989). Urea–NH3 –CO2 –H2 O:
VLE calculations using an extended UNIQUAC equation. Fluid Phase
5. Conclusion Equilibria, 53, 207.
Chen, H. S., & Stadtherr, M. A. (1985a). Simultaneous-modular approach
to process flowsheeting and optimization. Part I. Theory and imple-
The simulation procedure of HP urea synthesis loop is mentation. American Institute of Chemical Engineering Journal, 31,
developed in this work. The VLE of NH3 –CO2 –H2 O–urea 1843.
system was described in terms of the extended electrolytic Chen, H. S., & Stadtherr, M. A. (1985b). Simultaneous-modular approach
UNIQUAC equation. The units in HP urea synthesis loop to process flowsheeting and optimization. Part II. Performance on sim-
were simulated based on the equilibrium-stage model, and ulation problems. American Institute of Chemical Engineering Jour-
nal, 31, 1857.
the results were agreed well with the industrial design data. Chen, H. S., & Stadtherr, M. A. (1985c). Simultaneous-modular approach
The simultaneous-modular approach was applied to simulate to process flowsheeting and optimisation. Part III. Performance on
the synthesis loop, the advantage is that the model in flow- optimization problems. American Institute of Chemical Engineering
sheet level was simplified to be a set of linear equations, and Journal, 31, 1868.
these linear equations were resolved by alternately calling the Dente, M., Pierucci, S., Sogaro, A., Carloni, G., & Rigolli, E. (1988).
Simulation program for urea plants. Computers and Chemical Engi-
rigorous unit models until the coefficient matrices are conver- neering, 12, 389.
gent. The simulation results are compared with design data Dente, M., Rovaglio, M., Bozzano, G., & Sogaro, A. (1992). Gas–liquid
for plant. This work provides a useful tool for design of new reactor in the synthesis of urea. Chemical Engineering Science, 47,
process and retrofit of existing process. 2475.
992 X. Zhang et al. / Computers and Chemical Engineering 29 (2005) 983–992
Edwards, T. J., Maurer, G., Newman, J., & Prausnitz, J. M. (1978). ing an extended UNIQUAC equation. Chemical Engineering Science,
Vapor–liquid equilibria in multicomponent aqueous solutions of 41, 1185.
volatile weak electrolytes. American Institute of Chemical Engineer- Sander, B., Rasmussen, P., & Fredenslund, A. (1986b). Calculation of
ing Journal, 24, 966. solid–liquid equilibria in aqueous solutions of nitrate salts using an ex-
Irazoqui, H. A., & Isla, M. A. (1993). Simulation of urea synthesis reactor. tended UNIQUAC equation. Chemical Engineering Science, 41, 1197.
2. Reactor model. Industrial and Engineering Chemistry Research, 32, Satyro, M. A., Li, Y. K., Agarwal, R. K., & Santollani, O. J. (2001).
2671. Modeling urea processes: a new thermodynamic model and software
Isla, M. A., Irazoqui, H. A., & Genoud, C. M. (1993). Simulation of integration paradigm. http://www.cheresources.com.
urea synthesis reactor. 1. Thermodynamic framework. Industrial and Stamicarbon (1985). The know-how people, urea. London, UK: Parnell
Engineering Chemistry Research, 323, 2662. House.
Kotula, E. A. (1981). A VLE model of the NH3 –CO2 –H2 O–urea system Wei, S. A. (1994). Research and development on urea simulation system
at elevated pressure. Journal of Chemical Technology and Biotechnol- (in Chinese). Doctoral dissertation. Dalian University of Technology.
ogy, 31, 103. Westerberg, A. W., Hutchinson, H. P., Motard, R. L., & Winter, P. (1979).
Mei, A. H. (1994). Handbook of ammonia synthesis technology design. Process flowsheeting. Cambridge: Cambridge University Press.
Beijing: Chemical Industry Press (in Chinese). Yuan, Y., & Wang, W. S. (1997). Fertilizer engineering series: urea.
Nakamura, R. C., Bread, V. J. F., & Prausnitz, J. M. (1975). Thermody- Beijing: Chemical Industry Press (in Chinese).
namic representation of gas mixtures containing common polar and Zhang, X. P., Chen, H. S., Li, Y. K., Liu, X. Y., Yao, P. J., & Yuan, Y.
nonpolar components. Industrial and Engineering Chemistry, Product (2001). Simulation of urea reactor. Journal of Dalian University of
Research and Development, 15, 557. Technology, 41, 653 (in Chinese).
Peng, B. P. (1995). Chemical system analysis and modeling. Beijing: Zhang, X. P., Yao, P. J., Wu, D., & Yuan, Y. (2001). Simulation of urea
Chemical Industry Press (in Chinese). reactor of industry. Computational Methods in Multiphase, Series:
Sander, B., Fredenslund, A., & Rasmussen, P. (1986). Calculation of Advances in Mechanics, 29, 65.
vapour–liquid equilibria in mixed solvent/salt systems using an ex- Zhang, X. P., Zhang, S. J., & Yao, P. J. (2002). Simulation of high-
tended UNIQUAC equation. Chemical Engineering Science, 41, 1171. pressure urea synthesis loop. In The 47th Annual Safety in Ammonia
Sander, B., Rasmussen, P., & Fredenslund, A. (1986a). Calculation of Plants and Related Facilities Symposium.
vapor–liquid equilibrium in nitric acid–water–nitrate salt systems us-