Professional Documents
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PRO/II 9.3
Urea Plant
Casebook
May 2014
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Case 5:
Urea Plant
ABSTRACT
This case book demonstrates the use of PRO/II in the simulation
of a chemicals processing plant manufacturing 1000 tons per day of
urea from ammonia and carbon dioxide. Urea is widely used as a
solid fertilizer, as a protein supplement for livestock, as well as a
feedstock for the manufacture of plastics and adhesives. The
process plant simulated here includes a reactor, an NH3 recovery
distillation column, and a series of crystallizers. SIMSCISM's NRTL
databank, along with urea/water solubility data, provide a good
simulation of the system's vapor-liquid and solid-liquid equilibria.
Urea growth and nucleation rate crystallization data obtained from
the literature are provided for the crystallizer units.
Feature Highlights
Solids-Handling Application
User-supplied Solubility Data
Stoichiometric Reactor Units
Filtering Centrifuge Units
Solids Dryer and Freezer Units
Crystallizer Units with User-supplied Nucleation and Growth
Rates
Relevance
Urea has a maximum nitrogen content of 46% and, among major
nitrogenous fertilizers, is second only to ammonia. It also has the
highest nitrogen content of any solid fertilizer and can be easily
manufactured as granules. Worldwide, in 2002 a total of about 108
million metric tons (108Mt) of urea were produced in more than 70
countries. This production delivered about 51.4Mt of contained
nitrogen. China was the largest producer with about 28%, and all of
asia accounted for about 46% of the total. The United States
produced about 13%, or about 14Mt. Capacity in North America
and Western Europe is expected to decline due to fluctuating natural
gas prices. It is expected that production will continue to shift
toward world regions that have abundant natural gas, lower-cost
raw materials, and cheaper labor.
Routes to Urea
The production of urea may be divided into two separate parts:
Synthesis
Finishing
The synthesis loop produces a concentrated 70-80% urea solution.
The finishing step produces either granular urea or crystalline urea.
Spherical granules or flakes are formed by evaporation followed by
Process Outline
The urea process described in this case book produces a crystalline
product, and is based on information obtained from Chao1 and
Dente2. The urea process presented is intended as a generalized
example of a urea flowsheet and does not represent any specific
licensed technology. The urea flowsheet presented here is based on
the plant described by Chao1 for the Toyo Koatsu process, which is
a total NH3 recycle process. The urea synthesis plant modeled here
is a partial NH3 recycle process. A schematic of the process is
shown in Figure 5-1.
U
r
e
a
i
s
f
o
r
med by reacting CO2 and NH3 at high temperature and high
pressure to form ammonium carbamate urea, and water:
3NH 2 COONH 4 + NH 2 COONH 4
8NH 3 + 4CO 2 (5-1)
+3H 2 O
This highly exothermic reaction goes almost to completion under
reactor conditions of about 365 F and 3515 psia. The reactor
product stream pressure is let down through a pressure control valve
on the exit of the reactor. The reactor exit stream then enters the
NH3 recovery column where recovered NH3 is recycled back to the
reactor. The bottoms of the NH3 recovery column then enter the
high pressure decomposer where a small fraction of the ammonium
carbamate is decomposed and excess NH3 is removed as a vapor
stream:
NH 2 COONH 4 NH 2 CONH 2 + H 2 O (5-2)
This equilibrium endothermic decomposition reaction does not go
to completion under normal reaction conditions of 302 F and 325
Process Simulation
The complete input file for this simulation can be found in
Appendix 5-B. Selected portions of the input file are shown here.
For detailed explanations of the keywords used in the input file,
please refer to the PRO/II Keyword Manual, available from
Invensys.
KWM n appears beside some examples of keyword input. KWM indicates the
PRO/II Key Word Manual, Thermo indicates the PRO/II
Thermodynamic Data Input Manual, etc. n indicates the chapter
that provides detailed explanation of the keyword entries.
Component Data
All components except the intermediate, ammonium carbamate, are
in the SimSci databank. Ammonium carbamate is specified to be a
non-library component (using the NONLIB keyword). The particle
size distribution intervals for urea are given using the ATTRIBUTE
statement. The component urea is specified to exist in the vapor,
liquid, and solid phases using the PHASE statement.
KWM 6 COMPONENT DATA
LIBRARY 1, UREA / 2, WATER / 4, AMMONIA / 5, CO2 / &
6, N2 / 7, O2 / 8, H2, BANK=SIMSCI
NONLIBRARY 3, AMCA
PHASE VLS=1
ATTR COMP=1, PSD(MIC) 0, 20, 50, 100, 200, 500, 1000.
Thermodynamic Data
The NRTL liquid activity coefficient method is used to predict the
vapor-liquid equilibria, while the Soave-Redlich-Kwong equation
of state is used to calculate the liquid and vapor phase entropies.
Transport properties are calculated using the LIBRARY method.
User-supplied solubility data are used to predict solid-liquid
solubilities.
KWM 8 THERMODYNAMIC DATA
METHOD SYSTEM=NRTL, ENTROPY(V)=SRK, ENTROPY(L)=SRK,
&
KVALUE(SLE)=SOLDATA, TRANSPORT=LIBRARY
Solubility Data
With many inorganic systems, ideal solubility does not adequately
describe the solution behavior. For these cases solubility data can be
fitted to the following equation:
ln x i = A + B
---- + C ln T (5-3)
T
The above equation provides a good fit to much of the solubility
data reported in the literature. For systems containing more than
one solvent, the solubility of the solute in the multi component
solvent is calculated using the following relationship:
j=1
where:
xj
x j = ------------------- ji (5-5)
N
x
j
j = 1
Stream Data
Feed Streams
Data for the ammonia feed stream and the carbon dioxide feed
stream are provided as shown below.
KWM 9.1 STREAM DATA
PROP STRM=1, TEMP=-28, PRES=320, COMP(W)=4,105049
PROP STRM=2, TEMP=100, PRES=300, COMP(W)=5,93408
Recycle Streams
The composition, temperature, and pressure of the recycle stream
from the NH3 recovery column are estimated initially for the first
run through the simulation.
$ INITIAL GUESS FOR TEAR STREAMS
$
KWM 9.1 PROP STRM=7, TEMP=126, PRES=320, COMP(W)=2, 0.5 / 4, 58667.0
Reaction Data
The stoichiometry of the two reactionsthe primary urea reaction
and the decomposition reaction<%-2>is provided in the Reaction
Data category of input.
KWM 10.8 RXDATA
RXSET ID=RST1
REACTION ID=RXC1
STOICHIOMETRY 4,-8 / 5,-4 / 1,3 / 2,3 / 3,1
$
$ DECOMPOSITION REACTION
$
RXSET ID=RST2
REACTION ID=RXC2
STOICHIOMETRY 3,-1 / 4,2 / 5,1
Finishing
The bulk urea solution from the urea synthesis section is then sent
into the first stage (CR1) of a two stage vacuum evaporative
crystallization purification process. The crystallizer is operated at
130 F and 1.5 psia, and a design specification is made that 85% of
the urea in the feed crystallizes. Growth and crystal nucleation rate
data are provided using information obtained from the literature.
See the Kinetic Data section later in this case book for more
information on how these parameters were derived.
Kinetic Data
It is important to accurately determine growth and nucleation
kinetic parameters. The article by Bennett3 is a good source of urea
crystallization data. The articles by Bennett3 and Perry4 provide
good discussions on calculation of crystallization kinetic
parameters from crystal size distribution data.
Crystal size distribution data obtained from the Bennett3 article for
sample number 192 are used to demonstrate how to calculate both
growth and nucleation rates. First, the crystal size distribution data
in Tyler screen size are converted to average particle diameter.
From Figure 5-3, the intercept is 19.78 and the slope is -9.13. The
following calculations then are performed.
Since Dav= 1 mm and slope = -Dav/Gt
It follows that: Slope = -1/Gt = -9.13
The slope (-2.75) of the plot shown in Figure 5-4 yields a value of
-1.75 for the exponent i. The nucleation rate, B, then is obtained
from Equation 5-11 as:
k 1.75
B = Kb MT G (5-11)
Term Units
G velocity
Kg, constant velocity
SSRATIO, supersaturation dimensionless
Term Units
B No. / [(time) (liquid volume)]
Kb, constant No. / [(time) (liquid volume)]
MT liquid density
RPM revolutions per minute
The GEXPONENT term in Equation 5-13 is set to zero. The
following are converted growth and nucleation rates.
0.0324mm m ft h
G = K a = -------------------------- ---------------------- 3.28 ---- -------------- (5-15)
h 1000mm m 3600s
8 ft
= 2.952 10 ----
s
6 number of crystals L
B = 12.65 10 ----------------------------------------------- 28.32 -----3-
L-h ft
(5-16)
number of crystals-
8
= 3.582 10 ----------------------------------------------
3
ft h
Next, the Kb constant in the nucleation expression, Equation 5-14,
must be converted to be consistent with input units in the following
manner.
3 i
i g i i g 0.0624262lb ft
M T --- = M T --- -----------------------------------------
L L gL
(5-17)
lb i
M T -----3-
i i
= 0.0624262
ft
PRO/II Case Book Urea Plant 5-19
i m k k m 3.28ft k k ft k
G ---- = G ---- -------------- = 3.28 G ----
k
(5-18)
s s m s
No No L s
K b ------------ = K b ------------ 28.32 -----3- 3600 ---
L s L s h
ft (5-19)
3
= 101952K b Number of crystals/ft h
Conclusion
The 1000 tons/day urea process discussed in this case book
demonstrates the use of many chemicals and solids capabilities in
PRO/II. This example also highlights those features of PRO/II that
make it easy to incorporate available literature data.
Output Results
The keyword input file appears in Appendix 5-A. Appendix 5-B is a
listing of selected results. These include the urea reactor RX1 and
the decomposers RX2 and RX3, the filtering centrifuge units CEN1
and CEN2, the dryer DR1, the crystallizers CR1 and CR2, the
solids freezer FRZ1, and stream weight component rates for
selected streams.
Feeds 21
Products Liquid 22
Mixed 23
Operating Conditions
Temperature, F 130.0609
Pressure, PSIA 20.0000
Average Particle Diameter, MIC 648.4185
Average Solid Density, LB/FT3 83.3434
Total Solid Feed Mass Flow Rate, LB/HR 6.429E+04
Surface tension, DYNE/CM 69.3608
Volume Flow Rate of Filtrate, FT3/HR 589.9697
Particle Sphericity 0.7500
Physical Configuration
Cake Properties
Feeds 26
Products Liquid 27
Mixed 28
Operating Conditions
Temperature, F 130.0768
Pressure, PSIA 20.0000
Average Particle Diameter, MIC 567.6160
Average Solid Density, LB/FT3 83.3434
Total Solid Feed Mass Flow Rate, LB/HR 1.576E+04
Surface tension, DYNE/CM 69.4362
Volume Flow Rate of Filtrate, FT3/HR 257.6413
Particle Sphericity 0.7500
Physical Configuration
Cake Properties
Feeds 23 28
Products Vapor 29
Mixed 30
TEMPERATURE, DEG F 369.532
PRESSURE, PSIA 15.000
PRESSURE DROP, PSI 5.000
MOLE FRAC VAPOR 0.04528
MOLE FRAC TOTAL LIQUID 0.03534
MOLE FRAC H/C LIQUID 0.03534
MOLE FRAC FREE WATER 0.00000
MOLE FRAC MW SOLID 0.91937
MOISTURE CONTENT 9.99999E-04
DUTY, MM BTU/HR 10.55778
DRYER OPERATION MOISTURE-P
CRYSTALLIZER DATA
CRYSTAL COMPONENT 1 UREA
SUPERSATURATION 5.9605E-10
CRYSTAL SHAPE FACTOR 1.000
SLURRY PROPERTIES
FEED SLURRY LIQUID VOLUME FRACTION 1.000
FEED SLURRY VOLUMETRIC RATE, FT3/HR 1494.103
PRODUCT SLURRY LIQUID VOLUME FRACTION 0.452
PRODUCT SLURRY VOLUMETRIC RATE, FT3/HR 1406.645
PRODUCT SLURRY MAGMA DENSITY, LB/FT3 45.708
KINETICS DATA
GROWTH RATE, FT/SEC 2.9520E-08
NUCLEATION RATE, NUMBER/HR/FT3 4.9515E+07
Feeds 22
Products Vapor 24
Mixed 25
OPERATING CONDITIONS
TEMPERATURE, F 130.00
PRESSURE, PSIA 1.34
HEAT EXCHANGER DUTY, MM BTU/HR 5.5558
VOLUME, FT3 2318.0340
RESIDENCE TIME, HR 5.0517
CRYSTAL PRODUCTION RATE, LB/HR 15763.480
TEMPERATURE CHANGE IN HEAT EXCHANGER, F N/A
SLURRY RECIRCULATION RATE, FT3/HR N/A
AGITATOR RPM 100.000
CRYSTALLIZER DATA
SLURRY PROPERTIES
KINETICS DATA
Products Mixed 31
OPERATING CONDITIONS
TEMPERATURE, F 200.00
PRESSURE, PSIA 15.00
PRESSURE DROP, PSI 0.00
DUTY, MM BTU/HR -7.0614
MOLE FRAC VAPOR 0.0000
MOLE FRAC TOTAL LIQUID 0.0032
MOLE FRAC MW SOLID 0.9968
MELTING/FREEZING DATA
DUTY NMP
COMPONENTS FROZEN FRACTION MM BTU/HR F
--------------------- -------- ----------- -------
1 UREA 1.0000 -0.2976 270.86
INLET OUTLET
----------- -----------
FEED 3
4
LIQUID PRODUCT 5
TEMPERATURE, F 60.14 365.00
PRESSURE, PSIA 3515.0000 3515.0000
REACTION DATA
--------- RATES, LB-MOL/HR ---------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------ ----------- ----------- ----------- -----------
1 UREA 5.38249E-24 1591.8273 1591.8273
2 WATER 4.33234E-05 1591.8273 1591.8273
3 AMCA 1.7863 530.6091 532.3954
4 AMMONIA 9718.5395 -4244.8727 5473.6667 0.4368
5 CO2 2122.4364 -2122.4364 0.0000 1.0000
LB-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------ ----------- ----------- ------------
5 CO2 1 2122.4364 1.0000
(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED
REACTION DATA
--------- RATES, LB-MOL/HR ---------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------ ----------- ----------- ----------- -----------
1 UREA 1591.8272 0.0000 1591.8272
2 WATER 1591.8272 0.0000 1591.8272
3 AMCA 530.6146 -466.9409 63.6738 0.8800
4 AMMONIA 1922.5107 933.8817 2856.3924
5 CO2 0.0000 466.9409 466.9409
TOTAL 5636.7797 933.8817 6570.6614
LB-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------ ----------- ----------- ------------
3 AMCA 1 466.9409 0.8800
(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED
INLET OUTLET
----------- -----------
FEED 11
VAPOR PRODUCT 12
LIQUID PRODUCT 13
TEMPERATURE, F 158.00 252.00
PRESSURE, PSIA 25.0000 25.0000
REACTION DATA
--------- RATES, LB-MOL/HR ---------- FRACTION
COMPONENT FEED CHANGE PRODUCT CONVERTED
------------------ ----------- ----------- ----------- -----------
1 UREA 1591.7928 0.0000 1591.7928
2 WATER 1385.2013 0.0000 1385.2013
3 AMCA 18.3068 -18.2977 9.15342E-03 0.9995
4 AMMONIA 619.4463 36.5954 656.0417
5 CO2 23.1057 18.2977 41.4034
TOTAL 3637.8529 36.5954 3674.4483
LB-MOL/HR FRACTION
BASE COMPONENT REACTION CONVERTED CONVERTED(1)
------------------ ----------- ----------- ------------
3 AMCA 1 18.2977 0.9995
(1) FRACTION CONVERTED BASED ON AMOUNT IN FEED
STREAM ID 1 2 3 4
NAME NH3FD CO2FD
PHASE LIQUID VAPOR LIQUID LIQUID
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 5 6 7 8
NAME
PHASE LIQUID MIXED LIQUID LIQUID
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 9 10 11 12
NAME DECGS1 DECGS2
PHASE VAPOR LIQUID MIXED VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 13 14 15 16
NAME FLGS1 FLGS2
PHASE LIQUID VAPOR LIQUID VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 17 18 19 20
NAME CRYGS1
PHASE LIQUID LIQUID VAPOR MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 21 22 23 24
NAME CRYGS2
PHASE MIXED LIQUID MIXED VAPOR
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 25 26 27 28
NAME
PHASE MIXED MIXED LIQUID MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
STREAM ID 29 30 31
NAME DRYGS UREAPROD
PHASE VAPOR MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01
STREAM ID 20 21 23 25
NAME
PHASE MIXED MIXED MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
1 UREA
PSD, MIC
0.000 - 20.00 1.422E-06 1.422E-06 1.422E-06 4.925E-06
20.00 - 50.00 8.265E-05 8.265E-05 8.265E-05 2.719E-04
50.00 - 100.0 1.153E-03 1.153E-03 1.153E-03 3.492E-03
100.0 - 200.0 0.0136 0.0136 0.0136 0.0353
200.0 - 500.0 0.2314 0.2314 0.2314 0.3966
0.500 - 1.000 E+03 0.7537 0.7537 0.7537 0.5643
STREAM ID 26 28 30 31
NAME UREAPROD
PHASE MIXED MIXED MIXED MIXED
THERMO ID NRTL01 NRTL01 NRTL01 NRTL01
1 UREA
PSD, MIC
0.000 - 20.00 4.925E-06 4.925E-06 2.112E-06 2.112E-06
20.00 - 50.00 2.719E-04 2.719E-04 1.199E-04 1.199E-04
50.00 - 100.0 3.492E-03 3.492E-03 1.614E-03 1.614E-03
100.0 - 200.0 0.0353 0.0353 0.0179 0.0179
200.0 - 500.0 0.3966 0.3966 0.2639 0.2639
0.500 - 1.000 E+03 0.5643 0.5643 0.7164 0.7164