Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Save to My Library
Look up keyword
Like this
1Activity
0 of .
Results for:
No results containing your search query
P. 1
Modelling the Synthesis Section

Modelling the Synthesis Section

Ratings: (0)|Views: 14 |Likes:

More info:

Published by: Islam Hamdy Mohammed on Jun 26, 2012
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

06/26/2012

pdf

text

original

 
Chemical Engineering Journal 106 (2005) 249–260
Modeling the synthesis section of an industrial urea plant
Mohsen Hamidipour, Navid Mostoufi
, Rahmat Sotudeh-Gharebagh
Process Design and Simulation Research Centre, Department of Chemical Engineering, University of Tehran, P.O. Box 11365/4563, Tehran, Iran
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 sectionof an industrial urea plant. In the proposed model the urea reactor is divided into several continuously stirred tank reactors (CSTRs). It hasbeen considered in this study that formation of ammonium carbamate occurs through the heterogeneous reaction of carbon monoxide andammonia. 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 modelwas demonstrated using industrial data. It has been shown that there is a good agreement between the results of the model and the industrialdata. Dynamic response of the process to some important parameters in the synthesis section was also studied.© 2004 Elsevier B.V. All rights reserved.
Keywords:
Reactor modeling; Urea; Biuret; Heterogeneous reaction
1. Introduction
Urea (NH
2
CONH
2
) is produced at industrial scale bythe reaction between ammonia and carbon dioxide at highpressure (13–30MPa) and high temperature (170–200
C).There are different types of processes to produce urea in thecommercial units. These processes are typically called oncethrough, partial recycle and total recycle[1,2].In the total recycle process, which is employed widely, all the ammonialeavingthesynthesissectionisrecycledtothereactorandtheoverall conversion of ammonia to urea reaches 99%. Stami-carbonandSnomprogettiprocesses[3]arethemostcommonexamples of such process[4]. Since urea has became almostthemostwidelyusedfertilizeranditsproductionisimportantin the petrochemical industry, there has been many attemptsto model and simulate the reactor of urea production as theheart of the process[1–5].In the present work the entire urea synthesis section basedon the of stamicarbon process (including urea reactor, car-bamate condenser, stripper, and scrubber) is modelled. Ureaproduction consists of two reactions. In the first reaction,
Corresponding author. Tel.: +98 21 696 7781; fax: +98 21 695 7784.
 E-mail address:
mostoufi@ut.ac.ir (N. Mostoufi).
ammonia and carbon dioxide react to form ammonium car-bamate which decomposes to urea and water in the next step.In the previous works reported in the literature, the homoge-neousreactionbetweencarbondioxideandammoniatoformammonium carbamate is considered to take place in the re-actor. Since both carbon dioxide and ammonia are in the gasphase in the reactor and reaction between these two resultsin production of ammonium carbamate which is in the liquidphase, in the present study this reaction is considered to beheterogeneous. Moreover, in the studies reported in the lit-erature, biuret (NH
2
CONHCONH
2
) formation, which is themain undesired by-product in the urea production process,is neglected. As biuret is toxic to plants, its content in fertil-izers has to be kept as low as possible. It has been tried inthis work to model and validate the industrial urea synthesissection considering the above-mentioned reactions.
1.1. Process description
Synthesis section of stamicarbon process in the industrialurea production plant is shown inFig. 1. As it is seen in thisfigure, compressed carbon dioxide feed passes through thestripperalongwhichammoniaandcarbondioxide(duetode-compositionofammoniumcarbamateandfreedissolvedam-
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
Nomenclature
a
moles of water added per mole of ammoniumcarbamate
A0
initial concentration of A (kmolm
3
)
U0
initial concentration of urea (moll
1
)
density (kgm
3
)
 E 
activation energy (kJkgmol
1
)
molar flow rate (kgmolh
1
)
 H 
enthalpy (kJh
1
)
rate constant of urea production (h
1
)
rate constant of biuret production(lmol
1
h
1
)
p
equilibrium constant of ammonium carbamateproduction (atm
3
)
 M 
average molecular weight (kgkgmol
1
)
 N 
i
number of moles of component
i
(kgmol)
m
initial moles of carbon dioxide (kgmol)
n
initial moles of ammonia (kgmol)
n
t
total number of moles (mol)N/C nitrogen to carbon mass ratio
P
total pressure (atm)
P
c
critical pressure (kPa)
CO
2
partial pressure of carbon dioxide (atm)
NH
3
partial pressure of ammonia (atm)
Q
ac
heat produced by ammonium carbamate for-mation (kJh
1
)
Q
b
heat consumed by biuret formation (kJh
1
)
Q
c
heat exchanging duty of condensate in carba-mate condenser (kJh
1
)
Q
cw
heatexchangingdutyofcoolingwaterinscrub-ber (kJh
1
)
Q
u
heat consumed by urea formation (kJh
1
)
Q
s
heat exchanging duty of steam in stripper(kJh
1
)
A
reaction rate of component A(kgmolm
3
h
1
)
time (h)
temperature (K)
c
critical temperature (
C)
NBP
normal boiling point temperature (
C)
volume (m
3
)
v
0
volumetric flow rate of feed (m
3
h
1
)
 x
moles of ammonium carbamate (mol)
 X 
A
partial conversion of A
 X 
1
partial conversion of ammonium carbamate tourea
 X 
2
partial conversion of urea to biuret
 y
moles of urea per volume that reacts at
(moll
1
)
Subscript 
I inletO outlet
Table 1Properties of components[4]Component
NBP
(
C)
(kg/m
3
)
c
(
C)
P
c
(kPa)Urea 191
.
85 1230 431
.
85 9050Ammonium carbamate 600 1100 785
.
27 1103
.
92Biuret 598
.
3 1068
.
9 770
.
52 997
.
31CO
2
78
.
55 825
.
34 30
.
95 7370NH
3
33
.
45 616
.
07 132
.
4 11276
.
9H
2
O 100 997
.
99 374
.
15 22120O
2
182
.
95 1137
.
68
118
.
38 5080
.
02N
2
195
.
8 806
.
37
146
.
96 3394
.
37
monia)arestrippedofffromtheliquidphasetothegasphase.The gas flow from the scrubber which carries the stripped-off ammonia and carbon dioxide is then introduced into thetop of the carbamate condenser. Ammonia, together with thecarbamateoverflowfromthescrubber,isalsointroducedintothetopofthecarbamatecondenser.Thecarbamatecondenseris in fact a heat exchanger in which the heat generated duringcondensation of ammonia and carbon dioxide to form am-monium carbamate in the tube side is used to produce lowpressure steam in the shell side.Only part of ammonia and carbon dioxide condense in thecarbamate condenser and the rest react in the urea reactor inorder to supply the heat required for the urea production re-action. Liquid and gas phases leave the carbamate condenservia two separate lines to ensure a stable flow into the reactor.Ten trays are installed in the reactor in order to improve thecontact between the two phases. The liquid mixture in thereactor overflows into the stripper. The heat is supplied intothe stripper by the flow of saturated steam through its shell,resulting in decomposition of the remainder ammonium car-bamate into urea. The gas phase exiting the reactor containsfree ammonia and carbon dioxide as well as inert gas and isdischarged into the scrubber.In the scrubber, condensation of ammonia and carbondioxide is achieved. The heat of condensation is partly re-movedintheheatexchangingpartofthescrubberbycoolingwater. In the scrubbing part, remaining gases are scrubbedwith the lean carbamate solution. This stream, which is alow concentration aqueous solution of ammonium carba-mate, is a recycle from the low pressure section of the ureaprocess.
2. Model development
In this section the hypothesis and necessary equations fordeveloping the steady state and dynamic models of the ureasynthesis section are described. A complete list of the com-ponents involved in the process of urea synthesis as well astheir physical properties are shown inTable 1.
 
 M. Hamidipour et al. / Chemical Engineering Journal 106 (2005) 249–260
251Fig. 1. Block flow diagram in the synthesis section of stamicarbon urea plant.
2.1. Hypotheses
Simulation of the synthesis section of urea plant in thisstudy was done based on the following assumptions:
Only CO
2
, H
2
O, NH
3
and inert gases (O
2
, N
2
) exist in thegas phase.
CO
2
is not dissolved in the liquid phase. In fact, it couldonly be condensed with ammonia to form ammonium car-bamate in the liquid phase.
Formation of urea takes place only in liquid phase.
Dissolution of inert gases in the liquid phase is neglected.
Biuret is produced only in the reactor and the stripper.
2.2. Thermodynamics
In this study, the thermodynamic framework is based onthe model developed by Isla et al.[1]. However, Wilson andideal gas equations[6]were employed for calculating thethermodynamic properties of liquid and gas phases, respec-tively. A virtually identical model was presented by Agarwalet al.[7]where UNIQUAC was the model of choice. It isworth mentioning that many pairs of activity models and/orequations of state were examined to predict the thermody-namic behavior of the gas and liquid phases in this system.However, the closest results to the real plant data were foundwhen employing the above-mentioned pair of equations forpredicting the thermodynamic properties of the two phases.It should be noted that the main reactions in the urea synthe-sis process occur in the liquid phase (see Section2.3below).Therefore, the model is less sensitive to the choice of theequation of state employed for the gas phase.The Wilson equation was tuned for the urea synthesisconditions. The tuning was done by changing the interac-tion parameters such that the model prediction best fit theactual plant data. The complete list of temperature indepen-dent interaction parameters of Wilson equation are given inTable 2.
2.3. Reactions
The overall reaction of urea production is as follows:2NH
3
+
CO
2
NH
2
CONH
2
+
H
2
O (1)Theprocessofureasynthesisconsistsoftwosequentialsteps.In the first step, ammonium carbamate is formed by the re-action between ammonia and carbon dioxide:2NH
3
+
CO
2
NH
2
CO
2
NH
4
(l) (2)This reaction is very exothermic and fast in both directionsso that it could be considered at equilibrium at the conditionsfoundinindustrialreactorswheretheresidencetimeisratherhigh. In thenextstep, ammoniumcarbamateis dehydrated toform urea:NH
2
CO
2
NH
4
(l)
NH
2
CONH
2
(l)
+
H
2
O(l) (3)

You're Reading a Free Preview

Download
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->