Aspen Plus

Aspen Plus Urea Synthesis Loop Model

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Contents
1 Introduction .........................................................................................................1

2 Components and Units of Measurement ...............................................................2

3 Process Description..............................................................................................3

4 Physical Properties...............................................................................................5

5 Chemical Reactions Kinetics .................................................................................8

6 Simulation Approach ..........................................................................................10

7 Simulation Results .............................................................................................11

8 Conclusions ........................................................................................................13

9 References .........................................................................................................14

Contents iii
1 Introduction

This document describes the steady-state Aspen Plus model of the high-
pressure synthesis loop of a urea plant, with a capacity of about 1,100 metric
tons of prilled urea per year.
This simulation is based on the Stamicarbon CO2 Stripping Process, which is a
popular and fast growing process for manufacturing urea.
The work demonstrates the capability of Aspen Plus to rigorously model the
urea synthesis process. The modeling is complicated due to the formation of
ammonium carbamate, an intermediate product for which a special property
package has to be developed. This type of model is useful to analyze the plant
performance and to improve plant operation, including:
 Energy saving studies to improve economics of the plant.
 Studies of individual pieces of equipment with a view of increasing their
throughput and/or improving their performance.
 Flowsheet modification for better plant operation.
 Identifying bottlenecks.
 As a basis for optimization study and for developing on-line control system
of the plant.
While this document describes the simulation of the Stamicarbon CO2
stripping process, the accurate results obtained support the applicability of
Aspen Plus and the data package to other urea processes.

1 Introduction 1
2 Components and Units of
Measurement

The table below lists the components modeled in the simulation.

Component Name Component ID Type Formula

Water H2O CONV H2O

Ammonia NH3 CONV H3N
Carbon Dioxide CO2 CONV CO2
Urea UREA CONV CH4N2O
Ammonium Carbamate CARB CONV CH6N2O2
Nitrogen N2 CONV N2
Oxygen O2 CONV O2

A small amount of biuret (C2H5N3O2) is produced during the synthesis. In this

work, the biuret production is not considered, but the component can easily
be added if required.
The pure component properties of all the components except ammonium
carbamate can be retrieved from the Aspen Plus databanks. Special efforts
were made to incorporate pure component properties of ammonium
carbamate in the simulation.
A special contribution of this work is the development of a physical property
model to describe the simultaneous physical-chemical equilibrium occurring in
the urea-synthesis process.
Metric units are used in this work, except that temperature unit is oC,
pressure unit is kg/cm2 (abs), enthalpy flow unit is mmcal/hr, and mole flow
unit is kmol/day.

2 2 Components and Units of Measurement

3 Process Description

A simulation flowsheet of the synthesis loop is shown in Figure 1.

F01
FLASH2

R01 S15

E02
E03

S13

A01
RGIBBS
M01

MIXER

S01

E01

S07
SP1
A02 S12
RSTOIC SEP

Figure 1: Simulation Flowsheet of Urea Synthesis Loop

The high-pressure loop is operated at around 141 kg/cm2 (abs) and consists
of the following key pieces of equipment:
Equipment Purpose

R01 Urea Reactor, where ammonium carbamate is dehydrated to urea

E01 H.P. CO2 Stripper, where the bulk of the unreacted carbamate
from the reactor effluent is decomposed by stripping with CO2
gas and with heat input.
E02 H.P. Condenser, where the gaseous CO2 and NH3 condense and
react to form ammonium carbamate.
E03 H.P Scrubber, where the recycled carbamate solution from the
downstream low-pressure section is used to absorb unreacted
gases from the reactor.

3 Process Description 3
 The process is described as follows:
 Feed CO2 gas (S07) is fed to the CO2 stripper, E01, to strip the urea
solution coming from the reactor. In the stripper, ammonium carbamate
decomposes, liberating more NH3 and CO2 to be stripped out. Heat is
supplied on the shell side of tubes by condensing 285 psig steam while the
urea solution falls inside the tubes countercurrently down past the rising
CO2 stripping gas. The outlet liquid solution from the stripper is rich in
urea and goes to the downstream section for urea purification.
 In the adiabatic urea reactor, R01, an aqueous solution of NH3 and CO2
(much in the form of ammonium carbamate) and vapors flow upward
through 8 stages of reactor volume to minimize back-mixing and provide
enough residence time for urea formation. Remaining gases condense
and carbamate decomposes in the reactor to provide heat for the slightly
endothermic reaction of carbamate to urea. The urea solution (S06)
overflows from the top of the reactor back to the Stripper E01, while the
unreacted gases (S05) pass out the top of the reactor.
 These unreacted gases pass to the Scrubber, E03, where recycled
carbamate solution from the Evaporation/Recirculation section (S13) is
passed over the top of a packed bed and fills the tube side section of
vertical tubes. The gases rise up through the tubes and pass up through
the packed section before leaving the top of the vessel. The contact with
the carbamate solution absorbs the unreacted NH3 and CO2, while the
inert gases of O2, N2, and others (S15) vent out from the top. On the
bottom, recirculated cooling water flowing inside tubes removes the heat
of absorption from the carbamate solution. Carbamate solution (S17)
overflows out of the vessel.
 The solution (S17) together with the top vapor stream from the Stripper
(S08) is fed to the Carbamate Condenser, E02, through the use of an
ejector, where the ammonia feed (S01) serves as the pumping fluid.
Ammonium carbamate forms in this condenser. The vapor-liquid mixture
(S03) falls through tubes and the heat of reaction is removed by
generation of 50 psig steam on the shell side. The mixture goes to the
bottom of the reactor for urea production.
 The bottom stream (S09) from the Stripper E01 is sent to the downstream
section to recover urea. The recycled stream after recovering the urea
(S13) is back to the H.P. Scrubber to complete the loop.

4 3 Process Description
4 Physical Properties

The model for the thermodynamic properties of the NH3-CO2-H2O-UREA-

CARB-N2-O2 system is based upon the SR-POLAR model within Aspen Plus
(Soave, 1972; Peneloux and Rauzy, 1982; Schwartzentruber and Renon,
1989). The model uses an equation of state and is thus suitable for the high-
pressure, high-temperature conditions of urea synthesis. Further, the model
contains extensions that enable an accurate description of the phase and
chemical equilibria, the density and the other thermodynamic properties
(e.g., enthalpy) of this system.
We chose our approach to the modeling of the thermodynamic properties
after studying the previous modeling attempts in the literature and analyzing
the available data. Fréjacques (1948), Kawasumi (1952, 1953 and 1954) and
Lemkowitz (1980) developed chemical and thermodynamic models by
postulating reactions for urea formation and various simplified assumptions
for the phase non-ideality. The simplifying assumptions do not permit an
accurate and general model for the chemical-thermodynamic properties.
Bernadis et al. (1989) and Isla et al. (1993) developed improved theoretical
models by including ionic species and describing the nonideality of the liquid
phase by a modified UNIQUAC model. We believe that under the high
temperatures (160 to 200°C) and the relatively low water concentrations of
urea synthesis, the extent of ionization will be small. Further, modern
equations of state such as the SR-POLAR model are well suited to the
description of the thermodynamic properties of nonideal systems at high
pressures and temperatures. Thus we have chosen to use the SR-POLAR
model as the physical-property option.
Development of a data package for this system is difficult since most of the
data are only available as combined physical and chemical equilibria.
Disassociation pressure data are available for ammonium carbamate
(Janacke, 1930), which is the pressure at a specified temperature where
ammonia and carbon dioxide are in equilibrium with the condensed-phase
ammonium carbamate. Data are also available for the equilibrium conversion
of defined mixtures of NH3-CO2-H2O to urea (Kawasumi, 1952, 1953 and
1954; Inoue, 1972). Finally, bubble pressures have been measured for
defined mixtures of NH3-CO2-H2O at chemical equilibrium. The Aspen Plus
data analysis capabilities (DRS and DATA-FIT) have been used to obtain a
simultaneous good fit of these varied and complex sets of data.
Gorlovskii and Kucheryavyi (1979) have analyzed the urea conversion data
reported by many authors and have produced an empirical correlation that is
recognized to be accurate. Figure 2 compares the equilibrium conversions

4 Physical Properties 5
 predicted by the present AspenTech model with the Gorlovskii-Kucheryavyi
correlation. The present correlation clearly provides an accurate fit of the
data.

Figure 2: Equilibrium Conversion of CO2 to Urea at 170C Comparison of

Aspen Plus EOS to Correlation of Gorlovskii and Kucheryavyi (1980)

6 4 Physical Properties
 Figure 3 presents a comparison between the present AspenTech model and
the bubble pressure data measured by Lemkowitz (1971, 1972 and 1977).
The model provides an accurate description of the data and, in particular,
provides an accurate description of the minimum in bubble pressure, which is
necessary for an effective description of the urea synthesis process.

Measured and Calculated Bubble Pressures in the NH3-CO2 System

Comparison of ASPEN PLUS EOS to Data of Lemkowitz et al. (197x)
300

200°C
250
Bubble Pressure (bar)

200 180°C

150 160°C

100 140°C

50

0
0.65 0.70 0.75 0.80 0.85 0.90 0.95
Mole Fraction NH3 in Feed

Figure 3: Measured and Calculated Bubble Pressures in the NH3CO2 System

Comparison of Aspen Plus EOS to Data of Lemkowitz et al. (197x)
The AspenTech model provides an accurate description of the phase and
chemical equilibria related to urea synthesis. It also accurately describes the
other properties needed for reliable simulations, namely enthalpies and
densities.

4 Physical Properties 7
5 Chemical Reactions
Kinetics

There are two main reactions that take place in the urea synthesis process:
(1) 2NH3 + CO2  CARB
(2) CARB  UREA + H2O
The first reaction, which takes place in the liquid phase, converts ammonia
and carbon dioxide into ammonium carbamate. This reaction is highly
exothermic and fast. Chemical equilibrium is readily reached under the
operating conditions in the reactor. The second reaction also takes place in
the liquid phase and is endothermic. Its rate is slow and equilibrium is
usually not reached in the reactor.
A user subroutine, USURA.F, was developed to include the reaction kinetics of
both reactions. USURA.F is used in the reactor simulations. Both forward and
reverse reactions were considered. The kinetics of Reaction 1 has been set to
be rapid so that equilibrium is effectively reached. Limited literature data
were used for the kinetics of Reaction 2.
The reaction kinetics has been formulated to approach the equilibrium
composition for large residence times. The equilibrium has been described in
terms of the fugacity coefficients since an equation of state is used as the
thermodynamic model. The equilibrium constant for Reaction 1, in terms of
mole fractions, is written as follows:


K1  exp 

  G0
CARB  2GNH 3  GCO 2
0 0
  P   NH

22

3 CO 2


 0 
 
   CARB 
 RT  P

Where:
T = Temperature
P = Pressure
x = Mole fraction vector
R = Gas constant
P0 = Reference pressure (= 1 atmosphere)

8 5 Chemical Reactions Kinetics

 Gi0 = Ideal-gas Gibbs Free energy of component i at T, P0

i = Fugacity coefficient of component i at T, P, x

The equilibrium constant for Reaction 1 in terms of mole fractions is as
follows:
xCARB
K1  2
xNH3 xCO2

Similar equilibrium equations can be written for Reaction 2.

The rates for Reactions 1 and 2, in units of kmol/s/m3, are as follows:

 2 x 
Rate1  k1  xNH x
3 CO 2
 CARB 
 K1 

 xUREA xH 2O 
Rate2  k2  xCARB  
 K2 
The two rate expressions have been formulated so that they will necessarily
reach equilibrium at large residence times. The rate constant for Reaction 1
(K1) is set to a large value so that this reaction is essentially at equilibrium.
The rate constant for Reaction 2 determines the urea conversion in the
reactor. Only scant information is available to determine K2 and it is usually
best to adjust its value to fit plant data. A reasonable approximation for K2 is
the following:
 100.*106 
  
RT 
k2  15. 108 e /V L
Where R=8314.3 and VL is the molar volume of the liquid.

5 Chemical Reactions Kinetics 9

6 Simulation Approach

The CO2 Stripper, E01, is of the falling film type, which was approximated by
a RADFRAC (multistage distillation) block with 10 stages. Heat is supplied to
the stages 2-9 to simulate the heat transfer from the tubes. The urea
solution, falling down on tube walls, is stripped off volatile NH3 by the
entering CO2 gas (S07). On each stage the model considers the equilibrium
of carbamate in the liquid as well as the VLE of the mixture. Note that the
kinetics of carbamate formation is large enough to ensure that chemical
equilibrium for the carbamate reaction is reached in each stage of the
RADFRAC block.
The Urea Reactor R01, 7.52 ft in diameter and 95 ft in length, is modeled with
an RPLUG block. The kinetics is provided by the user subroutine USURA in
the RPLUG block.
In the reactor, the exothermic carbamate reaction and the endothermic urea
formation reaction are taking place. The reactor is designed such that its
volume is big enough for the desired urea production.
The H.P. Scrubber is modeled using a 5-stage RADFRAC block. Heat is taken
out from the bottom stage. Similar to the Stripper, E01, on each stage the
model considers the equilibrium of carbamate in the liquid as well as the VLE
of the mixture.
The E02 H.P. CO2 Condenser is modeled with an RSTOIC block. A Design
Specification paragraph is included to monitor the specified reactor outlet
temperature of 183oC by adjusting the extent of the carbamate reaction in
E02.
This simulation is based on a closed-loop flowsheet. The downstream section
is approximated by using a SEP block to link the Stripper bottom urea solution
(S09) to the recycled carbamate solution (S13).

10 6 Simulation Approach
7 Simulation Results

The Aspen Plus run was made using Version 206.5. Some of the results are
shown below, and a simulation flowsheet with stream data is shown in Figure
4. The simulation results of this generic model are reasonable compared with
similar plant operations.

Figure 4: Simulation Flowsheet of Urea Synthesis Loop

7 Simulation Results 11
 Key Process Simulation results:
Equipment Variable Value Unit

Heat duty 0 mmkcal/hr

R01 – Reactor Top temperature 183.0 (spec.) oC

Urea in exit stream 42,755 kg/hr

Heat duty 16.0 (spec.) mmkcal/hr
Top temperature 185.0 oC

Bottom temperature 165.5 oC

E01 – CO2 Stripper
Top stream (S08), 83,305 kg/hr
Bottom stream (S09), 76,745 kg/hr
Urea production 42,639 kg/hr
E02 - CO2 Heat duty -17.92 mmkcal/hr
Condenser Exit temperature 167 (spec.) oC

Heat duty -3.2 (spec.) mmkcal/hr

Top temperature 86 oC

E03 - Scrubber Bottom temperature 162 oC

Top stream (S15) 1602.2 kg/hr

Bottom stream (S17) 34,017.7 kg/hr

12 7 Simulation Results
8 Conclusions

 This urea process model has been developed using Aspen Plus Version
2006.5. This is a rigorous closed-loop model for the plant while the
recovery section is approximated by using a SEP model. The carbon
dioxide compression section is not included. From the results, it is shown
that the SR-POLAR property package used for simulation is appropriate.
 The model may be used as a guide for understanding the process and the
economics, and also as a starting point for more sophisticated models for
plant designing and process equipment specifying.
 For further refinement of the model, the following upgrades should be
made:
o The cooling water circuit for E03 and the low pressure steam circuit for
E02 should be implemented. This implementation is useful for energy
saving studies.
o E02 is simulated in this work by a RSTOIC model. However, a RPLUG
model is more suitable for the simulation of this equipment. However,
to do so, detailed equipment data for E02 are needed.
o The stripper E01 is a falling-film type equipment. It embodies VLE
equilibrium, mass transfer, reaction, and heat transfer. To rigorously
simulate this equipment, rate-based calculations (RateSep) should be
used. A special subroutine will be needed to incorporate the mass
transfer limitations of the falling-film. In this simulation, the RADFRAC
model was used with component efficiencies for NH3, CO2 and H2O as a
work around.
 The accurate results obtained in the present simulation indicate that
Aspen Plus and the physical property data package will provide accurate
simulations of other urea processes.

8 Conclusions 13
9 References

[1] Bernadis, M.; Carvoli, G.; Santini, M., “Urea-NH3-CO2-H2O VLE

Calculations Using an Extended UNIQUAC Equation,” Fluid Phase Equilibria,
53, 207-218 (1989).
[2] Fréjacques, M., “Theoretical Basis of the Industrial Synthesis of Urea,”
Chim. Ind., 60, 22-35 (1948).
[3] Gorlovskii, D.M.; Kucheryavyi, V.I., “Equation for Determination of the
Equilibrium Degree of CO2 Conversion During Synthesis of Urea,” Zh. Prikl.
Khim., 53, 2548-2551 (1979).
[4] Inoue, S.; Kanai, K.; Otsuka, E., “Equilibrium of Urea Synthesis. I.” Bull.
Chem. Soc. Japan, 45, 13339-1345 (1972).
[5] Isla, M.A.; Irazoqui, H.A.; Genoud, C.M., “Simulation of a Urea Synthesis
Reactor. 1. Thermodynamic Framework,” I&EC Research, 32, 2662-2670
(1993).
[6] Janecke, E., Z. Electrochem., 36, 645 (1930).
[7] Kawasumi, S., “Equilibrium of the CO2-NH3-Urea-H2O System Under High
Temperature,” Bull. Chem. Soc. Japan, 25, 227-238 (1952).
[8] Kawasumi, S., “Equilibrium of the CO2-NH3-Urea-H2O System Under High
Temperature and Pressure. II. Liquid-Vapor Equilibrium in the Loading Mole
Ratio of 2NH3 to CO2,” Bull. Chem. Soc. Japan, 26, 218-227 (1953).
[9] Kawasumi, S., “Equilibrium of the CO2-NH3-Urea-H2O System Under High
Temperature and Pressure. IV. Liquid-Vapor Equilibrium in the Presence of
Excess Ammonia or Carbon Dioxide,” Bull. Chem. Soc. Japan, 27, 254-259
(1954).
[10] Kotula, E.A., “Vapor-Liquid Equilibrium of the NH3-CO2-H2O-Urea
System at Elevated Pressure,” J. Chem. Technol. Biotechnol., 31, 103-110
(1981)
[11] Lemkowitz, S.M.; Goedegebuur, J.; van den Berg, P.J., “Bubble-Point
Measurements in the Ammonia-Carbon Dioxide System,” J. Appl. Chem.
Biotechnol., 21, 229-232 (1971).
[12] Lemkowitz, S.M.; van Erp J.C.; Rekers, D.M.; van den Berg, P.J., “Phae
Equilibria in the Ammonia-Carbon Dioxide Systems at and Above Urea
Synthesis Conditions,” J. Appl. Chem. Biotechnol., 30, 85-101 (1980).

14 9 References
 [13] Lemkowitz, S.M.; Vet, E.; van den Berg, P.J., “A Phase Model for the
Gas-Liquid Equilibria in the Ammonia-Carbon Dioxide Water-Urea System in
Chemical Equilibrium at Urea Synthesis Conditions. II. Experimental
Verification,” J. Appl. Chem. Biotechnol., 27, 335-348 (1977).
[14] Lemkowitz, S.M.; Vet, E.; van den Berg, P.J., “Phase Behavior in the
Ammonia-Carbon Dioxide System at and Above Urea Synthesis Conditions,” J.
Appl. Chem. Biotechnol., 22, 727-737 (1972).
[15] Peneloux, A.; Rauzy, E., “A Consistent Correction for Redlich-Kwong-
Soave Volumes,” Fluid Phase Equilibria, 8, 7-23 (1982).
[16] Schwartzentruber, J.; Renon, H., “Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equation of State,” I&EC Research,
28, 1049-1055 (1989).
[17] Soave, G., “Equilibrium Constants from a Modified Redlich-Kwong
Equation of State,” Chem. Eng. Sci., 27, 1196-1203 (1972).

9 References 15