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CPB30803

DESIGN PROJECT 2
(PLANT & PROCESS OPTIMIZATION)
L01-P10
JANUARY 2016
DESIGN A UREA PLANT WITH CAPACITY OF 100, 000
METRIC TONNES / YEAR
SUPERVISOR: MR SYAHIDI FADZLI ALFAN
SHARIFAH ADAWIYAH SYED IDRUS

55201113513

MUHAMAD NIZAMUDIN MUSTAFA

55201113601

MOHAMAD AZHAM SHAHARUDDIN

55201113660

SITI SYAZWANI MOHD NASIR

55201113584

MUHAMMAD IZZAT HAFIZUDDIN MOHD SHAH 55201214260

Designing Urea Reactor


Consideration Features in Chosen Type of Reactor
This process implicated the reaction between gas and liquid. The liquid mixture of NH 3
and carbamate (180C) and gaseous CO2 (140C) are fed to reactor. These two different phases
classified as heterogeneous reaction. They meet at 190C and 175 atm pressure inside the reactor
to form ammonia carbamate (NH2COONH4). The reaction taking place in the parameters of
reactor are as follows.
2NH3 + CO2 NH2COONH4 + Heat
(Exothermic reaction)

H = 136.23 kJ/mol

NH2COONH4 + Heat NH2CONH2 + H20


(Endothermic reaction) dehydration process

H = -17.57 kJ/mol

Overall reaction: 2 NH3 + CO2 NH2CONH2 + H20


(Exothermic reaction)

H = 118.66 kJ/mol

From the above reaction which occurs in the reactor, it can be identified as reversible
process. Whereby, the reaction between 2 mols of liquid NH3 and 1 mol of gaseous CO2 will
produce 1 mol of NH2COONH4 and 1 mol of H2O. This reaction will react reversely forming
back 2 mols of NH3 and 1 mol CO2. This reversible reaction basically evaluated at equilibrium
condition. Following are the kinetics parameter involving in the reaction inside the reactor.
However, this reaction considered as liquid phase reaction due to the outlet flow out from the
reactor in liquid form.
Table 1 Parameter in the reactor
Parameter
Working temperature
Design temperature
Working pressure
Design pressure
Ammonium carbamate conversion
Activation Energy, Ea
Frequency factor, A

Value
190C
250C
175 atm
210 atm
70%
60.93kJ/mol
5
-1
4.259 X 10 min

The reaction rate constant, k was determined by using Arrhenius equation


k =A e

Ea
RT

From the existence parameter, the value of k was calculated as follows.


k =( 4.259 X 10 5 min 1) e

60930J /mol
(8.314 J/ molK )(463.15 Kk )

k =0.05719 min

k =3.4314 hr1 (First order reaction)


The value and unit obtained drive to the first order of reaction. So, the appropriate rate law is
r A=k C A
This shows the reaction obeys a non-elementary Rate Law whereas the rate equation cannot be
determined by looking at the stoichiometric coefficient. Therefore, all the features obtained
correspond to plug flow reactor (PFR).

Figure 1 Plug flow reactor

Mass & Heat Balance of Reactor


Table 2 Mass Balance of each component inside reactor

Reactor
4

NH2COONH4 + heat NH2CONH2 + H2O


2NH3 + CO2 NH2COONH4 + heat

H = -17.57 kJ/mol
H = 136.23 kJ/mol

Table 3 Heat balance for Reactor

1. Total,
=1+2+3
=185330.5438 MJ/day
2. Ammonium Carbamate formation heat, 5
(117)
103
78

H5= 409.34477*

H5 = -614021.5741 MJ/day
3. Urea formation heat by decomposing Ammonium Carbamate, 6
H6 = 1060.256*15.5/60* 10^3
= 273899.4667 MJ/day
4. Energy generated in to reactor
Q==


out

= 273899.5744+185330.5438-614021.5841
= -154791.5744 MJ/day
Reactor Volume
Based on Table 2, inlet each component for the reactor are converted from T/Yr to kg/hr.
The values are as follows.
Table 4 Inlet reactor
Components
NH3
CO2
NH2COONH4

Inlet Reactor, T/Yr


102526.1973
24839.6430
147138.1395

Inlet Reactor, g/hr


10617.6
2572.39
16796.59

Determination of inlet volumetric flowrate, V0 for each component, density inlet must be
considered.
Table 5 Density Inlet
Components

Density (kg/m3)

NH3 (liquid)

618

CO2 (gas) at 40C


Ammonium carbamate

( Ref: J H Perry)

277.38

(density=PM/RT; P=162 atm,T=313 K)

1600

(Ref: http://www.inorganics.basf.com)

Following are the calculation and value of V0 for each components and total.
Table 6 Inlet volumetric flowrate
Components

Inlet volumetric flowrate,

V0

m3 /hr
NH 3

10617.6 kghr 1
618 kg m 3

17.181

V Bo , CO2

2572.39 kghr 1
277.38 kg m 3

9.274

V Co ,

16796.59 kghr 1
1600 kg m 3

10.498

V Ao ,

NH 2 COO NH 4
Total, V

36.953

Reactor Volume, V PFR


x

V PFR =F Ao
0

dX
r A

r A=k C A

C a=

F A F Ao (1X )
=
=C Ao ( 1X )
V
V0
x

V PFR =F Ao
0

V PFR =F Ao
0

V PFR =F Ao
0

dX
r A
dX
kCA
dX
k C Ao ( 1X )

F Ao x dX
V PFR =

k C Ao 0 (1X )

V PFR =

F Ao
1
ln
k C Ao
1x

V PFR =

Vo
1
ln
k
1x

V PFR =

36.953 m3 /hr
1
ln
1
10.7
3.4314 hr

]
[

]
7

V PFR =12.966 m

Residence time, t
t=

V
V0

t=

12.966 m3
36.953 m3 /hr

t=0.351 hr X

60 min
1hr

t=21.05 min

Mechanical design of the reactor


Materials for designing reactor
Ammonium Carbonate is one of chemical which is physically very corrosive. So
equipment and piping of High pressure (HP) synthesis section need to be constructed with a
corrosion resistant material. Moreover, stainless steels (SS) are the candidate materials
unfortunately conventional SS grades such as SS 304, SS 316 do not withstand with corrosion
due to carbonate. Before this, SS 316L UG (urea grade) was used with high amount of oxygen
supply. Coefficient of thermal expansion of this alloy is low (1.2 mm/m/100oC) compare to other
metals like steel (1.2 mm/m/100oC) making it perfect to use in industries (Brouwer, 2009)
Equipment used in urea process such as Urea reactor, Urea stripper, Carbonate condenser,
are constructed with Carbon steel lined or covered with a Protective layer of the above
mentioned Stainless steel materials. The thickness of the liner varies between 4 and 10 mm
(Brouwer, 2009). Welding is used as prominent method for fabricating such huge equipment.
Welding procedures are qualified by optimizing weld parameters in order to meet stringent. The
qualification is adopted for job, with appropriate quality checks in production welds also. Recent
developments in construction materials to curb corrosion mechanism operative in HP section is
also integrated.
Urea plant operates at high temperature / high pressure and carbonate solution, the
intermediate product is extremely corrosive. Ammonium carbonate at approximately 180-250C
and 180bar is extremely aggressive to materials. Candidate MOC for such aggressive
environments is Zirconium, Titanium, Duplex Stainless steel (SAFUREX & DP-28W) and
stainless steel (25Cr-22Ni-2Mo & 316L UG). Titanium had been used widely in the synthesis
reactor of the total recycle plants till early 1970s and the high pressure (HP) stripper of ammonia
stripping process till early 1990s. It has good passivation property with less passivation air.
However titanium is susceptible to erosion and it is difficult to weld. Other than that, The life
time of titanium is limited (Juneja, 2013).Due to this disadvantages, titanium has been gradually
taken over by stainless steel. Stainless steel has been widely used for this equipment in urea
plants. Stainless steel is almost immune to erosion and has good weldability but requires large
amount of passivation air for urea synthesis equipment compared to titanium. Type 316L UG has
been used for a long time in urea plants mainly because of its excellent weldability, fair corrosion
10

resistance and relatively low cost. Requirement of huge amount of passivation air by 316L UG in
synthesis and recycle sections restricts its operability.

Table 7 Advantages and disadvantages of material types

Type 25Cr-22Ni-2Mo SS is being used due to its better corrosion resistance than 316L
UG and excellent weldability. This type of metal has been used in reactor and strippers but it is
susceptible by chloride to SCC and costly. Duplex SS shows excellent corrosion resistance in
both Weld metal and HAZ. They possess better resistance to Stress Corrosion Cracking, hence
used in chloride environments as well. In oxygen free carbonate solutions, duplex has proved to
be more corrosion resistant than much more costly materials such as Titanium and high nickel
alloys. Various MOC used in urea plants worldwide, their advantages and disadvantages are
depicted in Table 1.

11

Accessories of the reactors


1. Cooling jacket.
There are different cooling jackets are available in the market depending the operating
conditions. However in order to find the right jacket, several factors need to be considered, for
example, cost, heat transfer rate required and pressure as a rough guide. Half pipe cooling jacket
can withstand pressure up to 70 bar (Sinnot & Towler, 2009, pp. 956-957) and less pressure drop
than other jackets. In order to fulfil the design operating conditions (140bar and 453K), half pipe
cooling jacket can be used as it can withstand high pressure. Standard sizes of the half pipe
jacket are 2 3/8, 3 and 4 -in.o.d. Thickness can be used as 3/16-in. for 2 3/8-in.od. and in
for both 3 and 4 1/2 in.od (McKetta, 1992, pp. 423-424) however cooling jacket diameter
and thickness can be slightly varied in order to accommodate the higher pressure and
temperature conditions and will be shown in the below calculations. Half pipe cooling jacket is
normally fabricated by 304 stainless steel to avoid problem like differential thermal expansion.

12

Heat transfer device


DESIGN OF AMMONIA PREHEATER
Ammonia inlet flow rate = 13.82503 kg/hr
Specific heat of ammonia = 5.14 KJ/kgC
Inlet ammonia temp.= 89.6F = 34 C
Outlet ammonia temp.= 338 F = 170 C
Heat required by ammonia, mc
= (13.82503 kg/ 3600 sec) * 5.14 KJ/kgC * (170-34) C
= 2.6845 KJ/sec
= 2.6845 KW
Latent heat of steam = 503.7 cal/mol= 2105.466 J/mol
Therefore, m*2105.466 = = 2.6845
m = (2.6845*1000)/2105.466
m = 1.27501 mol/sec =0.07082 kg/sec
LMTD = (T1 - T2) / ln(T1/T2)
= {(374 89.6) (374 338 )}/ ln (284.4/36) = 120.182
Area A = Q/(U*LMTD)
= (2.6845 *1000)/( 0.1435*120.182)= 155.658 m2
Choose 20mm O.D., 16mm I.D., 4.88m long tubes,
L= 4.83m
Area of one tube = 3.14*d*l= 3.14*4.83*(20/1000) = 0.303 m2
No.of tubes= 155.658/0.303 = 513
13

COLD FLUID TUBE SIDE


Mean ammonia temp.= (338+89.6)/2 =213.8 F= 101 o c
Tube cross-sectional area =(3.14/4)*162= 201mm2
Tubes per pass =no.of tubes/2 = 513/2 = 256.5 = 256
Tube flow area = (256*201)/1000000= 0.051m2
Ammonia mass velocity= 13.82503 /(60*60*0.051)= 0.075 kg/sec m2
Density of ammonia = 0.618 g/ml= 618 kg/m3
Ammonia linear velocity, ut= 0.075/618 = 1.21 x 10-4 m/sec

14

Instrumentation and Process Control


Level Control inside the Reactor ( Cascade Control )

Level Controller

Flow Controller

Output Valve

Output Flow Process

Reactor Level

Liquid level

Output Flowrate

Liquid Level

Reactor Level is affected by changes in output flow rate


Control Strategy: handle reactor level by adjusting the flow rate of the product output.
If a disturbance in output flow rate occurs, FC will act quickly to hold the output flow rate at its Set Point.
Control system measures Reactor level and compare it to set point level of the reactor. Then uses the resulting error signal as the input to a
controller for output flow rate.

Temperature Control inside the Reactor ( Cascade control )

Temperature Controller

Flow Controller

Steam Valve

Steam Flow Process

Reactor Temperature

Steam Flowrate

Temperature inside reactor

Reactor Temperature is affected by changes in reactant feed Temperature


Control Strategy: handle reactor temperature by adjusting the flow rate of the steam on the steam jacket.
Primary control loop (TT & TC)
Secondary (FT & FC)
The hot steam is used by MASTER controller (TC) to establish the set point for SLAVE loop controller.
Secondary measurement is fuel steam flow rate.
If a disturbance in steam supply occurs, FC will act quickly to hold the Steam flow rate at its Set Point.

Temperature
Level

Control system measures Jacket Temperature and compare it to set point temperature of the reactor. Then uses the resulting error signal as
the input to a controller for steam makeup.
PRINCIPAL: the 2ndmanipulated variable is located closed to potential disturbance & react quickly

Pressure control inside the Ractor ( Cascade control )

Pressure Controller

Gas Flow Controller

Gas Valve

Gas Flow Process

Reactor Pressure

Pressure Level

Gas Flowrate

Reactor Pressure

Reactor Pressure is affected by changes in gas flow rate


Control Strategy: handle reactor pressure by adjusting the flow rate of the gas.
If a disturbance in gas flow rate occurs, FC will act quickly to hold the gas flow rate at its Set Point.
Control system measures Reactor pressure and compare it to set point level of the reactor. Then uses the resulting error signal as the input
to a controller for gas flow rate.

Overall Process Control at Reactor

Heat Exchanger

Gas

Ammonia Ca

FC

Cascade is desired when the single loop performance is unacceptable and a measured
variable is available. Besides that, the secondary variable must indicate the occurrence of an
important disturbancein the system. Furthermore, the secondary variable also must have a
faster response than the primary which is 4 times faster than the primary in order to get a
better control.

ADVANTAGES OF CASCADE CONTROL


The cascade control is an improvement of the feedback and feed forward control
system because the conventional feedback usually take the corrective action for disturbance
after the control variable deviates from set point. Besides that, the feed forward requires to
calculate the disturbance explicitly and hence available to calculate the control variable.
Furthermore, employment of secondary measurement point and secondary feedback controller
are required for recognizes the upset condition sooner.
In conclusion, cascade control system are much more applicable in the reactor control
system because it have large improvement in performance when the
secondary is much faster than primary, simple technology with PID algorithms, use of
feedback at all levels since primary has zero offset for step-like disturbances.
Furthermore, plant operating personnel find cascades easy to operate because
cascade at one level cause all controllers above to become inactive.

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