Sintesis de Urea Con Aspen

Aspen Plus Urea Synthesis Loop Model
Contents
1Introduction...............................................................................1
2Components and Units of Measurement.......................................1
3Process Description....................................................................2
4Physical Properties.....................................................................3
5Chemical Reactions inetics........................................................5
!"imulation #pproach...................................................................$
$"imulation Results......................................................................$
%Conclusions................................................................................&
References.................................................................................1'
Aspen Plus Example Library
Proprietary Information of AspenTech
Unauthorized duplication or distribution strictly prohibited without prior written permission
i
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 !" Stripping Process, which is a popular and fast growing
process for manufacturing urea.
The wor# 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 pac#age has to be de$eloped. This type of model is useful to analy%e the plant
performance and to impro$e plant operation, including&
'nergy sa$ing studies to impro$e economics of the plant.
Studies of indi$idual pieces of e(uipment with a $iew of increasing their throughput and)or
impro$ing their performance.
*lowsheet modification for better plant operation.
+dentifying bottlenec#s.
As a basis for optimi%ation study and for de$eloping on-line control system of the plant.
,hile this document describes the simulation of the Stamicarbon !" stripping process, the accurate
results obtained support the applicability of Aspen Plus and the data pac#age to other urea processes.
2 Components and Units of Measurement
The table below lists the components modeled in the simulation.
Components
Component Name Component ID Type ormula
,ater -"! !./ -"!
Ammonia .-0 !./ -0.
arbon 1io2ide !" !./ !"
3rea 34'A !./ -5."!
Ammonium arbamate A46 !./ -7."!"
.itrogen ." !./ ."
!2ygen !" !./ !"
A small amount of biuret 8"-9.0!": is produced during the synthesis. +n this wor#, the biuret production
is not considered, but the component can easily be added if re(uired.
The pure component properties of all the components e2cept ammonium carbamate can be retrie$ed
from the Aspen Plus databan#s. Special efforts were made to incorporate pure component properties of
ammonium carbamate in the simulation.
A special contribution of this wor# is the de$elopment of a physical property model to describe the
simultaneous physical-chemical e(uilibrium occurring in the urea-synthesis process.
1
;etric units are used in this wor#, e2cept that temperature unit is
o
, pressure unit is #g)cm
"
8abs:,
enthalpy flow unit is mmcal)hr, and mole flow unit is #mol)day.
! Process Description
A simulation flowsheet of the synthesis loop is shown in *igure 1.
S05
S0<
S1"

S10
S19

S01
'0"
401
FLA!"
*01
'01
#T$I%
A0"
EP
SP1
#&I''
A01
'00
(I)E#
;01
%$"
Feed
%$"
tripper
*!+
Feed
#eactor
%arbamate
%ondenser
crubber
,ent
&as
Urea
olution
i"ure 1# Simulation lo$sheet of Urea Synthesis Loop
The high-pressure loop is operated at around 151 #g)cm
"
8abs: and consists of the following #ey pieces
of e(uipment&
%&uipment Purpose
401 3rea 4eactor, where ammonium carbamate is dehydrated to urea
'01 -.P. !" Stripper, where the bul# of the unreacted carbamate from the reactor
effluent is decomposed by stripping with !" gas and with heat input.
'0" -.P. ondenser, where the gaseous !" and .-0 condense and react to form
ammonium carbamate.
'00 -.P Scrubber, where the recycled carbamate solution from the downstream low-
pressure section is used to absorb unreacted gases from the reactor.
"
S05
S0< S1" S1 0 S19S01'0" 401FLA!"*01'01 #T$I%A0"EPSP1#&I' ' A0 1 '00(I)E#;01
%$"
Feed
%$"
tripper
*!+
Feed
#eactor %arbamate
%ondenser
crubber
,ent
&as
Urea
olution
The process is described as follows&
*eed !" gas 8S0<: is fed to the !" stripper, '01, to strip the urea solution coming from the
reactor. +n the stripper, ammonium carbamate decomposes, liberating more .-0 and !" to be
stripped out. -eat is supplied on the shell side of tubes by condensing "=9 psig steam while the urea
solution falls inside the tubes countercurrently down past the rising !" stripping gas. The outlet
li(uid solution from the stripper is rich in urea and goes to the downstream section for urea
purification.
+n the adiabatic urea reactor, 401, an a(ueous solution of .-0 and !" 8much in the form of
ammonium carbamate: and $apors flow upward through = stages of reactor $olume to minimi%e
bac#-mi2ing and pro$ide enough residence time for urea formation. 4emaining gases condense and
carbamate decomposes in the reactor to pro$ide heat for the slightly endothermic reaction of
carbamate to urea. The urea solution 8S07: o$erflows from the top of the reactor bac# to the
Stripper '01, while the unreacted gases 8S09: pass out the top of the reactor.
These unreacted gases pass to the Scrubber, '00, where recycled carbamate solution from the
'$aporation)4ecirculation section 8S10: is passed o$er the top of a pac#ed bed and fills the tube
side section of $ertical tubes. The gases rise up through the tubes and pass up through the pac#ed
section before lea$ing the top of the $essel. The contact with the carbamate solution absorbs the
unreacted .-0 and !", while the inert gases of !", .", and others 8S19: $ent out from the top. !n
the bottom, recirculated cooling water flowing inside tubes remo$es the heat of absorption from the
carbamate solution. arbamate solution 8S1<: o$erflows out of the $essel.
The solution 8S1<: together with the top $apor stream from the Stripper 8S0=: is fed to the
arbamate ondenser, '0", through the use of an e>ector, where the ammonia feed 8S01: ser$es as
the pumping fluid. Ammonium carbamate forms in this condenser. The $apor-li(uid mi2ture 8S00:
falls through tubes and the heat of reaction is remo$ed by generation of 90 psig steam on the shell
side. The mi2ture goes to the bottom of the reactor for urea production.
The bottom stream 8S0?: from the Stripper '01 is sent to the downstream section to reco$er urea.
The recycled stream after reco$ering the urea 8S10: is bac# to the -.P. Scrubber to complete the
loop.
' Physical Properties
The model for the thermodynamic properties of the .-0-!"--"!-34'A-A46-."-!" system is based
upon the S4-P!@A4 model within Aspen Plus 8Soa$e, 1?<"A Penelou2 and 4au%y, 1?="A
Schwart%entruber and 4enon, 1?=?:. The model uses an e(uation of state and is thus suitable for the
high-pressure, high-temperature conditions of urea synthesis. *urther, the model contains e2tensions
that enable an accurate description of the phase and chemical e(uilibria, the density and the other
thermodynamic properties 8e.g., enthalpy: of this system.
,e chose our approach to the modeling of the thermodynamic properties after studying the pre$ious
modeling attempts in the literature and analy%ing the a$ailable data. *rB>ac(ues 81?5=:, Cawasumi
81?9", 1?90 and 1?95: and @em#owit% 81?=0: de$eloped chemical and thermodynamic models by
postulating reactions for urea formation and $arious simplified assumptions for the phase non-ideality.
The simplifying assumptions do not permit an accurate and general model for the chemical-
thermodynamic properties. 6ernadis et al. 81?=?: and +sla et al. 81??0: de$eloped impro$ed theoretical
models by including ionic species and describing the nonideality of the li(uid phase by a modified
3.+D3A model. ,e belie$e that under the high temperatures 8170 to "00: and the relati$ely low
water concentrations of urea synthesis, the e2tent of ioni%ation will be small. *urther, modern e(uations
of state such as the S4-P!@A4 model are well suited to the description of the thermodynamic properties
of nonideal systems at high pressures and temperatures. Thus we ha$e chosen to use the S4-P!@A4
model as the physical-property option.
+
1e$elopment of a data pac#age for this system is difficult since most of the data are only a$ailable as
combined physical and chemical e(uilibria. 1isassociation pressure data are a$ailable for ammonium
carbamate 8Eanac#e, 1?00:, which is the pressure at a specified temperature where ammonia and
carbon dio2ide are in e(uilibrium with the condensed-phase ammonium carbamate. 1ata are also
a$ailable for the e(uilibrium con$ersion of defined mi2tures of .-0-!"--"! to urea 8Cawasumi, 1?9",
1?90 and 1?95A +noue, 1?<":. *inally, bubble pressures ha$e been measured for defined mi2tures of
.-0-!"--"! at chemical e(uilibrium. The Aspen Plus data analysis capabilities 814S and 1ATA-*+T:
ha$e been used to obtain a simultaneous good fit of these $aried and comple2 sets of data.
Forlo$s#ii and Cucherya$yi 81?<?: ha$e analy%ed the urea con$ersion data reported by many authors
and ha$e produced an empirical correlation that is recogni%ed to be accurate. *igure " compares the
e(uilibrium con$ersions predicted by the present AspenTech model with the Forlo$s#ii-Cucherya$yi
correlation. The present correlation clearly pro$ides an accurate fit of the data.
i"ure 2# %&uili(rium Con)ersion of C*2 to Urea at 1+,C Comparison of
Aspen Plus- %*S to Correlation of .orlo)s/ii and 0ucherya)yi 1123,4
-
*igure 0 presents a comparison between the present AspenTech model and the bubble pressure data
measured by @em#owit% 81?<1, 1?<" and 1?<<:. The model pro$ides an accurate description of the data
and, in particular, pro$ides an accurate description of the minimum in bubble pressure, which is
necessary for an effecti$e description of the urea synthesis process.
;easured and alculated 6ubble Pressures in the .-0-!" System
omparison of ASP'. P@3S '!S to 1ata of @em#owit% et al. 81?<2:
150G
170G
1=0G
"00G
0
90
100
190
"00
"90
000
0.79 0.<0 0.<9 0.=0 0.=9 0.?0 0.?9
;ole *raction .-0 in *eed
6
u
b
b
l
e

P
r
e
s
s
u
r
e

8
b
a
r
:

i"ure !# Measured and Calculated 5u((le Pressures in the N6!C*2 System
Comparison of Aspen Plus- %*S to Data of Lem/o$it7 et al8 112+94
The AspenTech model pro$ides an accurate description of the phase and chemical e(uilibria related to
urea synthesis. +t also accurately describes the other properties needed for reliable simulations, namely
enthalpies and densities.
: Chemical ;eactions 0inetics
There are two main reactions that ta#e place in the urea synthesis process&
81: ".-0 H !" A46
8": A46 34'A H -"!
The first reaction, which ta#es place in the li(uid phase, con$erts ammonia and carbon dio2ide into
ammonium carbamate. This reaction is highly e2othermic and fast. hemical e(uilibrium is readily
reached under the operating conditions in the reactor. The second reaction also ta#es place in the li(uid
phase and is endothermic. +ts rate is slow and e(uilibrium is usually not reached in the reactor.
A user subroutine, 3S34A.*, was de$eloped to include the reaction #inetics of both reactions.
3S34A.* is used in the reactor simulations. 6oth forward and re$erse reactions were considered. The
.
#inetics of 4eaction 1 has been set to be rapid so that e(uilibrium is effecti$ely reached. @imited
literature data were used for the #inetics of 4eaction ".
The reaction #inetics has been formulated to approach the e(uilibrium composition for large residence
times. The e(uilibrium has been described in terms of the fugacity coefficients since an e(uation of
state is used as the thermodynamic model. The e(uilibrium constant for 4eaction 1, in terms of mole
fractions, is written as follows&
( )
1
]
1
,
_
'

CARB
CO NH CO NH CARB
P
P
RT
G G G
K

"
"
0
"
0
0
"
0
0
0
1
"
e2p
,here,
T - Temperature
P - Pressure
2 - ;ole fraction $ector
4 - Fas constant
P
0
- 4eference pressure 8I 1 atmosphere:
0
i
G - +deal-gas Fibbs *ree energy of component i at T, P
0
i - *ugacity coefficient of component i at T, P, 2
The e(uilibrium constant for 4eaction 1 in terms of mole fractions is as follows&
"
"
0
1
CO NH
CARB
x x
x
K
Similar e(uilibrium e(uations can be written for 4eaction ".
The rates for 4eactions 1 and ", in units of #mol)s)m
0
, are as follows&
'

1
"
"
+ 1 1
K
x
x x k Rate
CARB
CO NH
'

"
"
" "
K
x x
x k Rate
O H UREA
CARB
The two rate e2pressions ha$e been formulated so that they will necessarily reach e(uilibrium at large
residence times. The rate constant for 4eaction 1 8C1: is set to a large $alue so that this reaction is
essentially at e(uilibrium. The rate constant for 4eaction " determines the urea con$ersion in the
reactor. !nly scant information is a$ailable to determine C" and it is usually best to ad>ust its $alue to fit
plant data. A reasonable appro2imation for C" is the following&
L
RT
v e k ) 10 J . 19
7
10 J . 100
=
"

,
_
,here 4I=015.0 and /

@
is the molar $olume of the li(uid.
/
< Simulation Approach
The !" Stripper, '01, is of the falling film type, which was appro2imated by a 4A1*4A 8multistage
distillation: bloc# with 10 stages. -eat is supplied to the stages "-? to simulate the heat transfer from the
tubes. The urea solution, falling down on tube walls, is stripped off $olatile .-0 by the entering !" gas
8S0<:. !n each stage the model considers the e(uilibrium of carbamate in the li(uid as well as the /@'
of the mi2ture. .ote that the #inetics of carbamate formation is large enough to ensure that chemical
e(uilibrium for the carbamate reaction is reached in each stage of the 4A1*4A bloc#.
The 3rea 4eactor 401, <.9" ft in diameter and ?9 ft in length, is modeled with an 4P@3F bloc#. The
#inetics is pro$ided by the user subroutine 3S34A in the 4P@3F bloc#.
+n the reactor, the e2othermic carbamate reaction and the endothermic urea formation reaction are
ta#ing place. The reactor is designed such that its $olume is big enough for the desired urea production.
The -.P. Scrubber is modeled using a 9-stage 4A1*4A bloc#. -eat is ta#en out from the bottom
stage. Similar to the Stripper, '01, on each stage the model considers the e(uilibrium of carbamate in
the li(uid as well as the /@' of the mi2ture.
The '0" -.P. !" ondenser is modeled with an 4ST!+ bloc#. A 1esign Specification paragraph is
included to monitor the specified reactor outlet temperature of 1=0
o
by ad>usting the e2tent of the
carbamate reaction in '0".
This simulation is based on a closed-loop flowsheet. The downstream section is appro2imated by using
a S'P bloc# to lin# the Stripper bottom urea solution 8S0?: to the recycled carbamate solution 8S10:.
+ Simulation ;esults
The Aspen Plus run was made using /ersion "07.9. Some of the results are shown below, and a
simulation flowsheet with stream data is shown in *igure 5. The simulation results of this generic model
are reasonable compared with similar plant operations.
0
i"ure '# Simulation lo$sheet of Urea Synthesis Loop
Cey Process Simulation results&
%&uipment =aria(le =alue Unit
;,1 > ;eactor
-eat duty 0 mm#cal)hr
Top temperature 1=0.0 8spec.:
o
3rea in e2it stream 5",<9" #g)hr

%,1 > C*2 Stripper
-eat duty 17.0 8spec.: mm#cal)hr
Top temperature 1=9.0
o
6ottom temperature 179.7

o
Top stream 8S0=:, =0,"0? #g)hr

6ottom stream 8S0?:, <7,<71 #g)hr
3rea production 5",707 #g)hr
%,2 ? C*2 Condenser
-eat duty -1<.?" mm#cal)hr
'2it temperature 17< 8spec.:
o
%,! ? Scru((er
-eat duty -0." 8spec.: mm#cal)hr
Top temperature =7.1
o
6ottom temperature 171.<

o
Top stream 8S19: 1707.1 #g)hr

6ottom stream 8S1<: 00,?=7 #g)hr
1
3 Conclusions
1. This urea process model has been de$eloped using Aspen Plus /ersion "007.9. This is a rigorous
closed-loop model for the plant while the reco$ery section is appro2imated by using a S'P model.
The carbon dio2ide compression section is not included. *rom the results, it is shown that the S4-
P!@A4 property pac#age used for simulation is appropriate.
". *or further refinement of the model, the following upgrades should be made&
a: The cooling water circuit for '00 and the low pressure steam circuit for '0" should be
implemented. This implementation is useful for energy sa$ing studies.
b: '0" is simulated in this wor# by a 4ST!+ model. -owe$er, a 4P@3F model is more suitable
for the simulation of this e(uipment. -owe$er, to do so, detailed e(uipment data for '0" are
needed.
c: The stripper '01 is a falling-film type e(uipment. +t embodies /@' e(uilibrium, mass transfer,
reaction, and heat transfer. To rigorously simulate this e(uipment, rate-based calculations
84ateSep: should be used. A special subroutine will be needed to incorporate the mass transfer
limitations of the falling-film. +n this simulation, the 4A1*4A model was used with component
efficiencies for .-0, !" and -"! as a wor# around.
0. The accurate results obtained in the present simulation indicate that Aspen Plus and the physical-
property data pac#age will pro$ide accurate simulations of other urea processes.
2
;eferences
K1L 6ernadis, ;.A ar$oli, F.A Santini, ;., M3rea-.-0-!"--"! /@' alculations 3sing an '2tended
3.+D3A '(uation,N *luid Phase '(uilibria, 90, "0<-"1= 81?=?:.
K"L *rB>ac(ues, ;., MTheoretical 6asis of the +ndustrial Synthesis of 3rea,N him. +nd., 70, ""-09 81?5=:.
K0L Forlo$s#ii, 1.;.A Cucherya$yi, /.+., M'(uation for 1etermination of the '(uilibrium 1egree of !"
on$ersion 1uring Synthesis of 3rea,N Oh. Pri#l. Chim., 90, "95=-"991 81?<?:.
K5L +noue, S.A Canai, C.A !tsu#a, '., M'(uilibrium of 3rea Synthesis. +.N 6ull. hem. Soc. Eapan, 59,
1000?-1059 81?<":.
K9L +sla, ;.A.A +ra%o(ui, -.A.A Fenoud, .;., MSimulation of a 3rea Synthesis 4eactor. 1.
Thermodynamic *ramewor#,N +P' 4esearch, 0", "77"-"7<0 81??0:.
K7L Eanec#e, '., O. 'lectrochem., 07, 759 81?00:.
K<L Cawasumi, S., M'(uilibrium of the !"-.-0-3rea--"! System 3nder -igh Temperature,N 6ull.
hem. Soc. Eapan, "9, ""<-"0= 81?9":.
K=L Cawasumi, S., M'(uilibrium of the !"-.-0-3rea--"! System 3nder -igh Temperature and
Pressure. ++. @i(uid-/apor '(uilibrium in the @oading ;ole 4atio of ".-0 to !",N 6ull. hem. Soc.
Eapan, "7, "1=-""< 81?90:.
K?L Cawasumi, S., M'(uilibrium of the !"-.-0-3rea--"! System 3nder -igh Temperature and
Pressure. +/. @i(uid-/apor '(uilibrium in the Presence of '2cess Ammonia or arbon 1io2ide,N
6ull. hem. Soc. Eapan, "<, "95-"9? 81?95:.
K10L Cotula, '.A., M/apor-@i(uid '(uilibrium of the .-0-!"--"!-3rea System at 'le$ated Pressure,N
E. hem. Technol. 6iotechnol., 01, 100-110 81?=1:
K11L @em#owit%, S.;.A Foedegebuur, E.A $an den 6erg, P.E., M6ubble-Point ;easurements in the
Ammonia-arbon 1io2ide System,N E. Appl. hem. 6iotechnol., "1, ""?-"0" 81?<1:.
K1"L @em#owit%, S.;.A $an 'rp E..A 4e#ers, 1.;.A $an den 6erg, P.E., MPhae '(uilibria in the
Ammonia-arbon 1io2ide Systems at and Abo$e 3rea Synthesis onditions,N E. Appl. hem.
6iotechnol., 00, =9-101 81?=0:.
K10L @em#owit%, S.;.A /et, '.A $an den 6erg, P.E., MA Phase ;odel for the Fas-@i(uid '(uilibria in the
Ammonia-arbon 1io2ide ,ater-3rea System in hemical '(uilibrium at 3rea Synthesis
onditions. ++. '2perimental /erification,N E. Appl. hem. 6iotechnol., "<, 009-05= 81?<<:.
K15L @em#owit%, S.;.A /et, '.A $an den 6erg, P.E., MPhase 6eha$ior in the Ammonia-arbon 1io2ide
System at and Abo$e 3rea Synthesis onditions,N E. Appl. hem. 6iotechnol., "", <"<-<0< 81?<":.
K19L Penelou2, A.A 4au%y, '., MA onsistent orrection for 4edlich-Cwong-Soa$e /olumes,N *luid
Phase '(uilibria, =, <-"0 81?=":.
K17L Schwart%entruber, E.A 4enon, -., M'2tension of 3.+*A to -igh Pressures and Temperatures by
the 3se of a ubic '(uation of State,N +P' 4esearch, "=, 105?-1099 81?=?:.
K1<L Soa$e, F., M'(uilibrium onstants from a ;odified 4edlich-Cwong '(uation of State,N hem. 'ng.
Sci., "<, 11?7-1"00 81?<":.
13

Sintesis de Urea Con Aspen

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Sintesis de Urea Con Aspen

Hochgeladen von

Copyright:

Verfügbare Formate

Aspen Plus Urea Synthesis Loop Model

model of the high-pressure synthesis loop of a

,here 4I=015.0 and /

3rea in e2it stream 5",<9" #g)hr

6ottom temperature 179.7

Top stream 8S0=:, =0,"0? #g)hr

6ottom temperature 171.<

Top stream 8S19: 1707.1 #g)hr

Das könnte Ihnen auch gefallen