Rapooorrrrrrrr 1

1.
INTRODUCTION
In this project, ammonia produced from synthesis gas, with nitrogen supplied from air
separation directly (Haber Bosch) process, with 1400 ton/year capacity in Sinop. Main
equipment: raw material and product tank, reactor, absorption column and distillation column
design; auxiliary equipment: heat exchanger, pump and compressor design is made. Reactor
conversion is 0.36 and overall yield is 0.45. These equipment purchase costs and utility costs
are calculated.
2. FLOWSHEET THAT TO BE DESIGNED

Ammonia Production
Production pathway:
Flowsheet:
Figure 1. Flowsheet that to be designed
Cost
Precaution
s
Risk
factors
Energy
Recovery
Catalyst
( Approximate Energy
consumption )
reactorType of
Utility Type
Type of operation
(bar) (in-out)Pressure
(in,out)(0C)Temperature
Performance
Code
Function
Equipment Name
Table1. Equipment Summary Table for Incomplete Conversion (Haber Bosch Process)
T-1
Syn Gas
Storage
Store syngas
under high
bar,22 C
22
Compre
ssor
To compress
and send
syngas to Heat
Exchanger
C-1
0.80
2832
11-22
Heat
Exchang
er
To heat syn
gas
E-1
2815
0
21
Adiabatic
Electricit
y
Steam
-16.24 kw
Toxical
Explosive
Flammabl
e
Storage
tank
should be
well
isolated.
High
Pressure
To
strength
Connectio
n nlet and
outlet
compresso
r
High c
Mediu
High
temp.
Shift
converte
r
CO+H2OCO
2+H2
H= - 41
kj/mol
R-1
Cooler
To Cool steam
which left
HTS
E-2
Low
temp.
Shift
converte
r
CO+H2OCO
2+H2
H= - 41
kj/mol
R-2
Xco=0.9
Xco=0.9
5
Expande Decrease
r
Pressure
C-2
Cooler
E-3
To cool steam
which left LTS
42
0
18
42
020
0
18
Isothermal
Isobaric
20
0
17
Isothermal
Isobaric
26
016
0
16-1
Adiabatic
Cataly Iron
st bed Oxide
Catalyst
Steam
Cooling
water
4.8 MJ for
keep
sothermal
conditions
To cool
Explosive
reactant
Flammabl
effluent
e
to
stabilizer
condition
*Thicknes
s of
reformer
wall is
increased
*Controlle
d
compositi
on H2 in
reactor
*Thicknes
s of
reformer
wall is
increased
*Controlle
d
compositi
on H2 in
reactor
Cataly Iron
st bed Oxide
Catalyst
Steam
2.1 MJ for
keep
sothermal
conditions
To cool
Explosive
reactant
Flammabl
ef fluent e
to
stabilizer
condition
Electricit
y
Mediu
Cost
Low
cost
Carbon
Removing
dioxide
Removal carbon dioxide
from synthesis
Unit
gas
A-1
Compre
ssor
To compress
C-3
0.75
5080
1-13
Heat
Exchang
er
To heat
E-4
8020
0
13
Methan
ation
CO+3H2CH4 R-3
+H2O
CO2+4H2CH
4+2H2O
Heat
Exchang
er
Compre
ssor
To heat steam
which is
leaving
Methanation
Unit
To compress
X=
0.99
X=
0.99
40
31
0
10
31
0
13-66
Adiabatic
Solvent :
%20
Monoeth
anolamin
e
Electricit
y
Adiabatic
Cataly Nickel
st bed
Catalyst
Process
flow(Out
let of
HTS)
Adiabatic
E-5
C-4
1.1 MJ To heat
the gas
mixture out of
CO2 removal
unit with HTS
outlet hot
stream
To cool
reactant
e ffluent
to
stabilizer
condition
Compre
ssor
Ammoni
a
Convert
er
To compress
C-5
Ammoni
a
Product
Storage
Tank
66150
Adiabatic
R-4
3H2+N22NH
3
H= - 46
kj/mol
Seperato To
distillate S-1
r
unconvered
synthesis gas.
Refriger
ation
35
0
Cooling the
effluent gas
out of
ammonia
converter.
X=0.26
42
5
0.99
75
150
Adiabatic
Multi
ple
cataly
st
beds
Ferric
Oxide
Catalyst
Process
flow(Out
let of
HTS)
1.8 MJ To heat
and compress
recycle stream
and output
stream of
methanation
unit
Steam
To cool
reactant
effluent
to
stabilizer
condition
s
Toxical
Explosive
Flammabl
e
Thickness
of
ammonia
converter
wall is
increased
High c
Storage
tank
should be
well
isolated.
High c
REF-1
Store
T-2
anhydrous
ammonia
under 1 bar,-33
C
40
-33
Toxical
Explosive
Flammabl
e
50
3. MATERIAL BALANCE
3.1. Degrees of Freedom Analysis
Molecular species balance
Degrees of freedom analysis = Number of unknown labeled variables
+ number of chemical reactions
- number of independent molecular species balances
- number of eqns relating unknown variables
3.2.Overall system
nCO
nN2
nCH4
nH2O
nCO2
nH2
Overall System
3H2+N2
2NH3
nH2
nN2
nCH4
nH2O
nCO
nCO2
Flow Diagram of Overall System for Ammonia Process
Unknowns : 6 (nH2, nN2, nCH4, nH2O, nCO, nCO2) (+)
Chemical reaction : 2(+)
Molecular species balances :6 (nH2, nN2, nCH4, nH2O, nCO, nCO2) (-)
Eqns relating unknown variables: 2 (-)
NDf= 6+2-6-2 = 0
Water 2.58 tmole/h

CO2 5.61 tmole/h
O2 0.67tmol/h
MEDIUM PRESSURE PROCESS
8.917 tmole/h
OVERALL SYSTEM
Synthesis Gas
57 % H2
5.71tmol/h
29 % CO
Product,P
10.7% CO2
%99.9 NH3
3.3 % CH4
Air 3.26 tmole/h
CH4 3.030 tmol/h
79% N2
21% O2
Reactions:
CO+H2O
CO2 + H2
CO2+4H2
CH4 + 2H2O
CO+3H2
CH4 + H2O
3H2+N2
2NH3
Calculations:
Molecular Spieces Balances
Yield=%100
Table 2. Molecular Spieces Balance Equations

CO2 BALANCE
nCO = (8.9170.107)+ 1 2
8
H2O BALANCE
N2 BALANCE
H2 BALANCE
NH3 BALANCE
O2 BALANCE
CH4 BALANCE
CO BALANCE
nH2O = 2.58 1+ 2 2 + 3
nN2=3,260.79 + 4
nH2=(8.9170.57 )+ 14 2 3334
nNH3=+2 4
nO2=3.260.990.21
nCH4= (8.9170.033) 2 3
nCO= 8.9170.29 1 3 =0
2.410,107= 4
8.9170.29 1 3 =0
8.9170.29 = 1+ 3 1+ 3 = 2.585
8.9170.57= 1+ 42+33+ 33
8.9170.033= 2 3
nO2=3.260.990.21=0.67
%99 Conversion of CO2 from CO2 Removal
(8.9170.1070.99)( 8.9170.1071.0)= 1+ 2
%99 Conversion of CH4 from Seperator 2
(8.9170.0330.99) (8.9170.0331.0)= 2 + 3
1=5,61393
2= 2.965 10-3
3= 3,028
4= 1.69
24= 3.38
Table3. Input And Output Streams
nCO
nH2O
nN2
nH2
Input Stream Flowrate(tonmole/h)

2.58
2.58
2.58
5.08
9
Output Stream Flowrate(tonmole/h)

0
0
0
0
nNH3
nO2
nCH4
nCO2
0
0.680
0,29
0,95
3.38
0.670
3.030
5.61
3.3. Material Balance for Each Equipment

3.3.1. Material Balance for Reactor
T=350 C
P=150 bar
Conversion=0.45
nT
10.6176tonmo
l/h
xi
xi
ni
H2
7.71
0.726
CH4
0.330
0.0311
3H2+N2
2NH3
CH4
x1
H2
x2
N2
x3
NH3
CH4 Balance
0.330 = nT(x1)
H2 Balance
7.71x0.55 =nT(x2)
N2 Balance
2.57x0.55 = nT(x3)
NH3
10
1-(x1+x2+x3)
nT (nT.x1+nT.x2+nT.x3) = 2.313
(2.313tonmol/h)x(24h/1 day)x(17g/1mol ammonia) = 943.704 ton/day NH3
3.3.2. Material Balance for Absorber
T=40 C
P=15 bar
Conversion=0.99 of CO2 get absorbed by MEA
CO2
n1
3.255tonmol/h
11.497tonmol/
h
n2
xi
xi
H2
0.686
H2
x1
CH4
0.0255
CH4
x2
CO2
0.286
CO2
x3
CO
x4
CO
0.00112
H 2O
+x4)
H 2O
%99 CO2 get absorbed

11.497x0.286x0.99=n1
n1 =3.255 tonmol/h
Overall
n1+n2 = 11.497
11
1-(x1+
3.255+n2 = 11.497
n2 = 8.241 tonmol/h
CO Balance
11.497x0.00112 = 8.241x(x4)
X4=0.00156
H2 Balance
11.497x0.686 =8.241x(x1)
X1=0.957
CH4 Balance
11.497x0.0255 = 8.241x(x2)
X2 = 0.0355
CO2 Balance
11.497x0.286=(3.255)+8.241x(x3)
X3=0.004
H2O
1-(0.004+0.0355+0.957)
XH2O =0.0035
3.3.3. Material Balance for Distillation Column
12
F=D+B
7.967 tmol/h = 5.63 tmol/h +B
B = 2.33 tmol/h
Ammonia Balance;
7.967* 0.29 = 2.33 *XB + 5.63 * 0,0088

xB,Ammonia = 0,978
Hydrogen Balance;
7.967* 0.53 = 2.33 * 0,0175 + 5.63 * xD,hydrogen

xD,methanol = 0,74
Nydrogen Balance;
7.967 * 0.17 = 0,0141* 0.00605 + 5.63 * xD,Nydrogen

xDNydrogen = 0.24
13
Table 4. Stream Summary Table

Component
Tempareture (0C)
Pressure (atm)
Mass Flowrate
(kmol/h)
Phase
y (i)
Air Seperation inlet
Air
200
50
3.16
Gas
AirSeperation Outlet
Air
200
50
3.16
Gas
CO
H2
CH4
CO2
H2O
CO
H2
CH4
CO2
H2O
CO
H2
CH4
CO2
H2O
CO
H2
CH4
CO2
H2O
420
18
Gas
420
18
2585.9
5082.69
294.26
954.12
2585.9
199.74
5733.6
227.38
2541.35
201.52
199.74
5733.6
227.38
2541.35
201.52
12.88
7886.94
293.17
3288.1
13
0.29
0.57
0.033
0.107
0.29
0.0224
0.643
0.0255
0.285
0.0226
0.0224
0.643
0.0255
0.285
0.0226
0.00112
0.686
0.0255
0.286
0.00113
Stream
HTS inlet
HTS outlet
LTS inlet
LTS outlet
17
200
17
200
14
Gas
Gas
Gas
CO2 Removal inlet
CO2 Removal outlet
Methanation inlet
Methanation outlet
Ammonia Converter
inlet
Ammonia Converter
outlet
CO
H2
CH4
CO2
H2O
CO
H2
CH4
CO2
H2O
CO
H2
CH4
CO2
H2O
H2
CH4
H2O
N2
H2
CH4
N2
H2
CH4
NH3
60
14
12
40
310
10
310
10
350
125
425
125
12.88
7886.94
293.17
3288.1
13
12.86
7886.64
292.56
32.96
28.84
12.86
7886.64
292.56
32.96
28.84
7768.8
332.8
198.37
113.058
4.105
Gas
Gas
Gas
Gas
Gas
1.142
406.474
15
Gas
0.00112
0.686
0.0255
0.286
0.00113
0.00156
0.957
0.0355
0.004
0.0035
0.00156
0.957
0.0355
0.004
0.0035
0.936
0.0401
0.0239
0.965
0.035
0.0028
0.9972
4.CALCULATION OF EQUIPMENTS
4.1 STORAGE
Unless the raw materials (also called feed stocks or feeds) are supplied as intermediate
products (intermediates) from a neighboring plant, some provision will have to be made to
hold several days or weeks worth of storage to smooth out fluctuations and interruptions in
supply.[1] Most processes require storage for the feed and product. Storage of feed is required
if the delivery of the feed is in batches (e.g. barge, rail car, road truck).
In design of some pressure vessels, safety is the primary consideration and the design is a
compromise between considerations of economy and safety. The possible risk of a given form
of failure is balanced against the effort required for its prevention, the resulting design should
be achieved an adequate standard of safety at minimum cost.[2]
4.1.1.Reasons of Chosen Values
Operational temperature for storage tank is determined as ambient temperature so there is no
need to use utility. According to table of climatic data[App 1][3], Maximum value (25 C) is
selected as operating temperature in order to provide technical flexibility for storage tank.
By using molliere diagram specific volume versus storage pressure graph is drawn at
maximum value of ambient temperature.
16
Graph 1.:Specific Volume versus Storage Pressure graph at max value of Tambient for
syntesis gas
Specific volume decreases with increasing pressure continiously on the graph. However,After
10 atm,the effect of increasing pressure on decrease in specific volume becomes a lot less and
thickness of walls of storage tank is increased.Decrease in specific volume after 11 atm may
tolerate thickness but more importantly very high pressure can cause risk factors to bring out
so there is no need to get into this high pressure area.Therefore,11 atm is selected as operating
pressure.In conclusion,sytesis gas is stored in gas phase under our conditions.
Why stainless steel material ?

Stainles steell becasue of corrosive effect of ammonia and methane.
Why 3 hours synthesis gas residence time?
No need for long time storage

We can get fluid anytime we want
Weekends and holidays may delay transportation
But if a problem occurs, system cannot stop, so we have chosen 3 hours.
Why 12 hours ammonia residence time?
No need for long time storage
Factory close to market

Weekends and holidays may delay transportation
Why closed tank for synthesis gas storage ?
Methane is volatile and easily flammable
Dead Volume Reason
Particles from the tank due to corrosiveness of methane or ammonia.
17
4.1.2.Storage Calculations
4.1.2.1.Sample Calculations for Syntesis Gas Storage Tank
Design Basis of Storage Tank
Location
Residence Time(hours)
Operating Temperature(C)
% Safety Factor/Design Temperature(C)
Operating Pressure(atm)
% Safety Factor/Design Pressure(atm)
Minumum Discharge Pressure(atm)
Material Construction
Tank Shape
Number of tank
Sinop
3
Ambient (25C)
%10 / 27.5C
11
%10 /12.1
1
Stainless Steel
Spherical closed tank
11
Size of storage tank (raw material storage)

Mass flow rate of synthesis gas = 8.917 tmol/h
Safety factor of tank = %10
Density of synthesis gas =7.28 kg/m3
Volume of gas :
Vgas 8.917
tmol 1000kmol 14.96kg

m3
x
x
x
x3h 58793m3
h
1tmol
1kmol 7.28kg
Total volume of the tank:

VTank = 58793 m3 x ( 1 + 0.1 ) = 64672m3
11 tank;
64672/11=5879 m3
4
Vtan k 5879m3 r 3
3
r = 11 m
18
Surface area of tank:

ATank 4 r 2 1520m2
Thickness of Storage Tank

For spherical tank;
[1]
ri
2
or
P 0.385
.S.Ej
P.ri
Cc
S .E j 0, 6.P
Ej: efficiency of joints expressed as a fraction

P: Maximum allowable internal pressure, kPa (gauge)
ri: inside radius, m
S: maximum allowable working stress, kPa
Cc: corrosion allowance
Pdesign = 12.1 atm, Tdesign = 27.5 0C
ri = 11 m (storage radius)
S = 121395 kPa
Ej = 0.85
t
[1]
[1]
1226 11
Cc
(121935 0.85) 0.6(1226)
t = 0.13 m =13 cm
19
Cost of Tank
Material Cost (Purchased Cost of Storage Tank):
After searching the literature of material selection, we choose stainless steel.
The cost of stainless steel tank is found = 243000
Installation Cost (%40 of P.Cost)
243000 x 0.40 = 97200
Cost of painting :
Price of painting : 1/1m2
Painting surface area 1520 m2
Cost of painting = 1520m2 x
= 1520
Total cost of tank = cost of material + cost of painting + cost of installation

= 243000 + 1520 +97200 = 341720
4.1.2.2.Sample Calculations for Ammonia Storage Tank
20
Design Basis of Storage Tank

Location
Residence Time(hours)
Operating Temperature(C)
% Safety Factor/Design Temperature(C)
Operating Pressure(atm)
% Safety Factor/Design Pressure(atm)
H/D
Minumum Discharge Pressure(atm)
Material Construction
Tank Shape
Number of tank
Sinop
12
Ambient (25C)
%10 / 27.5C
12
%10 /13.2
1.2
1
Stainless Steel
Cylindrical
4
Size of storage tank (product storage)

Mass flow rate of ammonia = 1400 ton/day
Safety factor of tank = %10
Density of ammonia =599.2 kg/m3
Volume of liquid :
ton 1000kg 1day

m3
Vliq 1400
x
x
x
x12h 1168m3
day
1ton
24 h 599.2kg
Total volume of the tank:
VTank = 1168 m3 x ( 1 + 0.1 ) = 1285m3
4 tank;
1285/4=321 m3
If H/D = 1.2
Vtan k 321m3
D3
4
21
1 3
4 Vt
H

= 7.4 m
H=8.88m
Surface area of tank:
ATank
2 D 2
DH
292m 2
4
Thickness of Storage Tank

For cylindirical tank;
[1]
ri
2
or
P 0.385
.S.Ej
P.ri
Cc
S .E j 0, 6.P
Ej: efficiency of joints expressed as a fraction

P: Maximum allowable internal pressure, kPa (gauge)
ri: inside radius, m
S: maximum allowable working stress, kPa
Cc: corrosion allowance
Pdesign = 13.2 atm, Tdesign = 27.5 0C
ri = 3.7 m (storage radius)
S = 94500 kPa
[1]
22
Ej = 0.85
t
[1]
1333.2 3.7
Cc
(94500 0.85) 0.6(1333.2)
t = 0, 063 m = 6,3 cm
The tank is covered with stainless steel profiles which are 1,5m*6m.[2]
Total number of needed profiles = (Area of the cylindrical tank)/(Area of a profile)
= (2 * * 3.72 + 2 * * 3.7 * 8.8) / 9 +2
= 34 profiles .
Total cost = ( number of the profile) ( volume of the profile )
( density of steel) ( cost of the profile )
Total cost = (34) * (1,5 * 6 * 0,014459 )m3 * (7848 ton/m3) * (614 /ton)
= 21156
Cost of Tank
Material Cost (Purchased Cost of Storage Tank):
After searching the literature of material selection, we choose stainless steel.
The cost of stainless steel tank is found = 21156
Installation Cost (%40 of P.Cost)
21156 x 0.40 = 8462.4
Cost of painting :
Price of painting : 1/1m2
Painting surface area 292 m2
Cost of painting = 292m2 x
= 292
Total cost of tank = cost of material + cost of painting + cost of installation

23
= 21156 + 292 +8462.4 = 29910
Size of the Tank:

Assume H/D = 1.2 ,calculated H=8.8 m and D = 7.4 m is determined.
Table 5. Risks of Storage Tanks

Where
Risk Type
Cause of Risk
Precaution of
Risk
Cost
Synthesis gas
Storage tank
Operational
safety risk/fire
risk
Compact of
connection
equipment.
Medium
Synthesis gas
Storage tank
Hazardous
effect/ CO
leakage
Hazardous
effect
Amount of H2
overcome upper
limit in case of
leakage.
Amount of
CO>50ppm
Purchased
dedector
Low
Human healty
Purchased
dedector
Low
Product storage
tank
24
Table 6. Specification Sheet of Raw and Product Material Storage Tank

Identification
Identification
Item: Syntesis Gas Storage Tank
Item:Ammonia Storage Tank
Function: Raw Material Storage
Function: Product Material Storage
Location: Sinop
Location: Sinop
Type: Spherical Closed Tank
Type: Horizontal/Cylindrical
Total Flow Rate of Syntesis Gas): 8.917 Total Flow Rate of Ammonia : 1400
tmol/ h
ton/day
Composition: 57% H2,29%CO,10.7%CO2, Composition: 99.9% NH3

3.3%CH4
Phase: Gas
Residence Time: 3 hours
Safety factor:%10
Number of Tank: 11
OperationalTemperature/Pressure
Phase: Liquid
Residence Time: 12 hours
Safety factor:%10
Number of Tank: 4
: OperationalTemperature/Pressure:
Ambient (250C)/11atm
Ambient (250C)/12 atm
Design Temperature/Pressure: 27.50C/12.1 Design Temperature/Pressure: 27.50C/13.2
atm (1+safety factor)
Material: Stainless Steel
Tank Radius (m) :11
Wall Thickness(m): 0.13
Volume of One Tank(m3): 5879
Cost for tank, : 341720
Restriction:
atm (1+safety factor)

Material: Stainless Steel
TankDiameter/Height(m):7.4/8.8 (H/D:1/2)
Wall Thickness(m): 0.063
Volume of One Tank(m3):321
Cost for tank, : 29910
Restriction:
For gases, consider pressure cylinders
and small horizontal cylindrical tanks
for pressures > 800 kPa.
H/D : 1.2-2.1[4]
Number of storage <12[4]
4.2.REACTOR (AMMONIA CONVERTER)

Design Basis 1st reactor
Pop. - Top. :
Xa1 :
150 bar - 425C

0.19
25
Operational Type:
Reactor Type:
Toperating < 500 C (for nonactive of
catalyst)
Feed Ratio(N2:H2):
Maximum P :
h/D:
Partical Size:
Adiabatic
Fixed Bed
1:3
75 kPa
2.5
4 mm
Design Basis 2nd Reactor

Pop. - Top. :
Xa1 :
Operational Type:
Reactor Type:
catalyst)
Feed Ratio(N2:H2):
Maximum P :
h/D:
Partical Size:
150 bar - 300C

0.058
Adiabatic
Fixed Bed
1:3
75 kPa
2.5
4 mm
Design Basis 3rd Reactor

Pop. - Top. :
Xa1 :
Operational Type:
Reactor Type:
catalyst)
Feed Ratio(N2:H2):
Maximum P :
h/D:
Partical Size:
150 bar - 200C

0.058
Adiabatic
Fixed Bed
1:3
75 kPa
2.5
4 mm
26
4.2.1.Calculations
Thermodynamically Equilibrium Calculations
1
3
N 2 H 2 NH 3
2
2
CP a bT cT 2 DT 3
NH3=-4619 J/gmol
G0298= -16450 J/gmol
G=-RTlnK298
LnK298=6,639564864
Energy Balances
1st Reactor
input output generation consumption accumulation
Assume that the system is adiabatically work;
0 (for adiabatic )
QR(by flow) + Qrem.(by the wall) = QGeneration
27
QR = QG
1. Reactor
F .Cp .dT F .Cp .dT (H

TR
T1 f
T0
298
390
( NH 3 ) o
).Fi0 . X i
.C P NH 3 F( N 2 )0 Cp( O2 ) F( H 2 ) 0 Cp( H 2 ) F( CH 4 ) Cp( CH 4 ) .dT
298
( N 2 )0 .
390
( N2 ) 0
298
( N2 ) 0
( N 2 )0 .
390
.Cp( N 2 ) F( H 2 )0 .Cp( H 2 ) F(CH 4 ).CpCH 4 dT X A. F( N 2 )0 .
.Cp( N 2 ) F( H 2 )0 .Cp( H 2 ) FCH 4 .Cp(CH 4 ) .dT X A . F( N 2 )0 .Cp( N 2 ) 3F( N 2 )0 .Cp( H 2 ) 2 F( N 2 )0 .Cp( NH 3 ) .dT
( N 2 )0
390
390
Cp( N 2 ) 3F( N 2 )0 .Cp( H 2 ) 2 F( N 2 )0 .Cp( NH 3 ) .dT
298
298
2Cp
( N 2 )0 .
( NH 3 )
298
Cp( N 2 ) F( H 2 )0 .Cp( H 2 ) F(CH 4 ) .CpCH 4 .dT X A .F( N 2 )0 . Cp.dT

298
Cp( N 2 ) F( H 2 )0 .Cp( H 2 ) F(CH 4 ).Cp(CH 4 ) .dT F( N 2 )0 .Cp( N 2 ) F( H 2 )0 .Cp( H 2 ) F(CH 4 ) .Cp(CH 4 ) .dT
XA
(1 X A ).Cp( N 2 ) ( F( H 2 )0 3F( N 2 ) 0 . X A ).Cp( H 2 ) ( F( NH 3 ) 0 2 F( N 2 ) 0 . X A .Cp( NH 3 ) ) FCH 4 .CpCH 4 dT
( N 2 )0
298
TR
(29 + 0.2199x10 -2 T + 0.5723x10 -5 T 2 - 2.871x10 -9 T 3 )dT
390
28
Cp( N 2 ) 3Cp( H 2 ) .dT
CH 4
.(34.31 + 5.469x10 -2 T + 0.3661x10 -5 T 2 - 11x10 -9 T 3 )dT
390
+
T
( H 2 )0
.(28.84 + 0.00765x10 -2 T + 0.3288x10 -5 T 2 - 0.8698x10 -9 T 3 ).dT
390
2Cp
( H R ).FN 2 . X A FN 2 . X A
( NH 3 )
Cp( N 2 ) 3Cp( H 2 ) dT
298
FN 2 . X A .(Cp.dT )
T
188,8 x(29 + 0.2199x10 - 2 T + 0.5723x10 -5 T 2 - 2.871x10 -9 T 3 )dT

390
3,05 x(34.31 + 5.469x10 -2 T + 0.3661x10 -5 T 2 - 11x10 -9 T 3 )dT

390
566,7x (28.84 + 0.00765x10 -2 T + 0.3288x10 -5 T 2 - 0.8698x10 -9 T 3 )dT

390
F( N 2 ) 0 . X A .H R
(Cp.dT )
298
T
(5475,2 0,415T 1,08x10
T 2 5,47 x10 7 T 3 )dT
T 2 3,36 x10 8 T 3 )dT
390
(104,65 0,17T 1,12 x10
390
T
(16343,6 433,5.T 1,86 x10
.T 2 4,93x10 7 T 3 )dT
390
X A H R ,T .
=188,8
.(
)
29
188,8. X A .(-81164 - 45.22T + 0.0283T 2 - 0.2248x10 -5 T 3 - 1.9729x10 -9 T 4 )
41615776 21932T 21705T 2 9,83 x10 4 T 3 2,68 x10 7 T 4
X A 15323763 8535,5T 5,34T 2 4,24 x10 4.T 3 3,73 x10 7 .T 4
XA
41615776 21932T 217,05T 2 9,83x10 4 T 3 2,68 x10 7 T 4

15323763 8535,5T 5,34T 2 4,24 x10 4.T 3 3,73 x10 7 .T 4
*Constant Rate Curve Calculations
k1 PN 2
P
PH 21.5
-k 2 NH1.53
PNH 3
PH 2
c:
density of catalyst
k1=1.79*104e-87090/RT
k2=2.57*1016e-198464/RT
FA0 1 X Ae
FA0 1 X Ae FB 0 3FA 0 X Ae 2 FA 0 X Ae 0.028225806 FA 0
YA=
3FA0=FB0
FA 0 1 X Ae
FA0 1 X Ae 3 X Ae 0.028225806
YA
30
1 X Ae
4.0282258026 2 X Ae
YA
YB=3YA
X Ae
2.014112903 X Ae
YC=
P.YA P.YB
P.YC
1.5
2.57*1016.e 198464 / RT
P.YC
1.5
P.YB
= 1.79*104e-87090/RT
R= 8.314 J/gmolK
YA YB
P
YC
1.5
1.5
2.57 *1016 e23871.06086 / T
1 YC
P 0.5 YB
= 1.79*104e-10475.10224/T
YB=3YA
YA
YC
2.5
2.57 *1016 e 23871.06086 / T
YC
1.5
20 3 YA
1
0.5
= 1.79*104e-10475.10224/T.(20)1. 5.(3)1. 5.
1 X Ae
r c 1.79* 10 .e
4
10475.10224 / T
20 3
1.5
1.5
4.0282258026 2 X Ae
X Ae
2.014112903 X Ae
31
2.5
1.5
2.57 *1016.e 23871.06086 / T .
20 3
0.5
X Ae
2.014112903 X Ae
1.5
1 X Ae
4.02822558026 2 X Ae
1.5
r c 1.79* 10 e
4
10475.10224 / T
20 3
1.5
2
0.5
1.5
20 3
1.5
2.57 *1016 e 23871.06086 / T
1.5
2.5
1 X Ae
r c 147.0635* 10 e
0.31281*10 e
16
10475.10224 / T
23871.06086 / T
X Ae
2.014112903 X Ae
1.5
1 X Ae
2.014112903 X Ae
1 X Ae
1
X Ae 2.014112903 X Ae 1.5
X Ae 2.014112903 X Ae
1 X Ae
2.5
2.014112903 X Ae
X Ae
2.014112903 X Ae
2.5
0.5
1.5
*2. and 3.reactor calculations are same as the 1. reactor.
32
First Reactor
XA1
1/RA
Volume
3.64
0.032
56860.6
0.063
46571.7
0.095
31338.2
0.127
20969.8
0.158
16580.9
0.190
79329.5
Second Reactor
XA2
1/RA
Volume
0.190
80917.9
2.04
0.200
69986.9
0.210
61903.1
0.219
56864.9
0.229
55467.8
0.239
60832.0
0.248
90104.5
Third Reactor
XA3
1/RA
Volume
0.248
90104.5
2.46
0.256
79932.5
0.286
65223.2
33
0.315
53651.1
0.333
50011.5
0.348
42362.3
0.360
39812.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
450
500
550
600
650
700
750
Graph 2.Kf-T grafii
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
450
550
650
750
850
Graph 3..Xae-T grafii
34
950
1050
0.8
0.7
0.6
r=0
r=0,1
0.5
Ra
r=0,5
0.4
r=1
r=1,5
0.3
r=3
0.2
r=5
r=10
0.1
0
550
r=20
600
650
700
750
800
850
900
950
1000
T(K)
Graph 4. Ra-T grafii
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
480
530
580
630
680
730
780
830
Graph 5 .1/ra Xa grafii

V1'
V1
(1 )
35
880
930
980 1030 1080 1130 1180
V1'
3.64
m3
( 1 0.4 )
= 6 m3
V2'
V2
(1 )
V2'
2.04
m3
( 1 0.4 )
'
V 3=
= 3.4 m3
V3
m3
(1 )
= 4.1 m3
FUNCTION
OPERATING TYPE
REACTOR OPERATING
CONDITIONS
REACTION
FEED RATIO
MOLAR FLOW RATE(tmol/h)
Production of ammonia from syntesis gas

Adiabatic
Outlet temperature
425 C
Operational pressure
150 atm
N2+3H22NH3
H2/ N2 = 3/1
Recycle Ratio =0.60
Inlet stream
N2
7.76
36
CO/CO2
H2
H2O
CH4
0.36
Converion
-/15.54
3.57
5.33
REACTOR SETTING
Residence time <1 s
Iron(III) oxide catalyst particle size between (050)mm
Reactor diameter between =(1.6 -3)m
Height/catalyst particle diameter H/Dp >100 and
Dp/D <0.10
Usually bed volume porosity 0.42 which decreases to
0.38 as the bed ages.
90% conversion within a reactor length of bed
height/catalyst particle diameter = 100
Material of construction
CATALYST PROPERTIES
Total cost(All of the reactors)
p is <1 to 10% of total pressure; if Dp too high then

use larger catalyst
Carbon steel
Catalyst type
Void fraction
Density
Purity
Partical diameter
Melting point
483170 $
Iron(III) oxide
=0.42
5242kg/m3
%99.99
0.004 m
1566 oC
Table 8.Risks of Reactors

Where
Risk Type
Cause of Risk
37
Precaution of
Risk
Cost
Inlet of
ammonia
converter
Operational
safety risk/fire
risk
There is a glate
risk because of
amount of H2
overcome upper
limit in case of
leakage
High Pressure
Srengthening of
the connection
equipment.
Medium
In ammonia
converter
Operational
safety
risk/explosion
Increasing the
Wall thickness.
Low
In ammonia
converter
Operational
flexbility/
Catalyst
poisoning
Because of high
temperature and
inert materials
Medium
In ammonia
converter
Operational
flexbility/
Pressure drop
Use catalyst
smaller than
1mm.
Cold feed or
intercooling for
high temp. and
use Al2O3-K2OCaO besides
catalyst for inert
materials
Using 1-2mm
catalyst.
In ammonia
converter
Operational
flexbility/
channelling
Flow stoppage.
Using 1-2mm
catalyst.
Medium
4.3.SHIFT CONVERTERS
38
Medium
In the water gas shift reactor, CO reacts to form H2. Reactor type was determined
with respect to be low volume of reactor and economic.Also at exist ammonia synthesis
plants,using catalytic Multi-Tubular Reactor. Total tube height was calculated as 23.5m ,
so multi-tubular was used as each one height is 3m.Then the operating conditions were
selected and reactor volume, size and cost were calculated.
Water 2.58 tmol/h
F=8.917 tmol/h
F = 11.497 tmol/h
Reactor
FCO
FCO2
0.29
FCO
0.0224
0.107
FCO2
0.285
FH2O
0.0241
FH2
0.57
FH2
0.643
FCH4
0.033
FCH4
0.0255
Desgn Bass Of Water Gas Shft Reactor

Reactor Type
Catalytic Multi-Tubular Reactor
Reactor Operation Type
Adiabatic
39
Reactions Conversions
0.91
Catalyst
Cu/Zn
Catalyst Density, Porosity
Density = 6877 kg/m3

Porosity = 0.3
Feed Ratio (H2O/CO)
47400
RCO 2,96 105 exp
RT
PCO PH 2 O
PCO 2 PH 2
Ke
Reactions in Water Gas Shft Reactor
CO H 2 O
CO2 H 2
1atm
H 25
41,16
0
C
Graph 6. Constant Rate CurvesTin = 150 0 C
40
kj
mole
Graph 7. Adiabatic lines on constant rate curve
XB = 0.91
Tf = 261 0 C
Graph 8. -1/RB XB at Operation Curve
Volume: 7.7 m3
41
Reactor Szng
Design Basis
Dp
0,1
D
h
100
Dp
( P ) B
=3000 Pa/m
Dp = 3 mm
=1.742 10-5 Pas

= 6.0437 kg/m3 = 0.3
Calculations were given in the Appendix 3 detailed.
ID = 0.5 m
H = 23.5 m
Calculaton Of Catalyst Amount

Catalyst amount (1 ) xV
kg
x(1 0,3) x7, 7 m3
3
m
Catalyst amount 37067 kg catalyst
Catalyst amount 6877
42
HIGH TEMPERATURE SHIFT CONVERTER REACTOR SPECIFICATION SHEET

Item no
R-1
Function
Water gas shft reaction
Operating
Continous, adiabatic
Kinetic reactor, Mlti-Tubular Reactor
Type
High temperature shift
Total Flow rate (inlet)
8.917 tmol/h
Total Flow rate (outlet)
11.497 kmol/h
Pressure
19 atm
350-420 0C
Temperature (inlet-outlet)
Head material
Stainless steel
Pressure drop
0,5 bar
CO (g) + H2O(g) > CO2 (g) + H2 (g)
Reaction
Conversion of carbon monoxide
Catalyst type
0,99
Fe2O3 containing %5-10 Cr2O3, 0,5 void frac., 1g/cm3
density, 170 m2/g urface area
Feed ratio( CO/H2O)
1:1
Component composition % mol
Inlet
outlet
H2O
100
2.41
CO
29
2.24
CH4
3.3
2.55
C02
10.7
28.5
H2
57
64.3
Reactor Size
Vtotal=7.7 m3
tube)=3m
Total reactor purchased cost

2005
ID=0.5m
Htotal=23.5m
179374$
43
H(one
Installation factor (% ?of

Purchased cost)
0.5
Installed cost
89687 $
LOW TEMPERATURE SHIFT CONVERTER REACTOR SPECIFICATION SHEET

Item no
R-2
Function
Water gas shft reaction
Operating
Kinetic reactor, Multi-Tubular Reactor
Type
Low temperature shift
11.49 tmol/h
11.497 tmol/h
Pressure
17 atm
210-3000C
Temperature (inlet-outlet)
Head material
Stainless steel
Pressure drop
0,5 bar
CO (g) + H2O(g) > CO2 (g) + H2 (g)
Reaction
Conversion of carbon monoxide
Catalyst type
0,90
%40-45 Copper Oxide - %20-30 Zinc Oxide the balance
being ammonia, 0,5 void frac., 1g/cm3 density, 170 m2/g
urface area
inlet
outlet
CH4
2.55
2.55
CO
2.24
0.112
H2O
2.26
0.112
C02
28.5
28.6
H2
2.26
68.6
Reactor Volume
2 m3
Total reactor purchased cost

2005
89687$
Installation factor (% ? of
0.5
44
Purchased cost)
Installed cost 2005
44844 $
Table 10. Risks of HTS and LTS

Where
Risk Type
Cause of Risk
Precaution of
Risk
Cost
In HTS and LTS Operational

reactors
flexbility/ CO
Leakage
Because of
higher activity
Using smaller
catalyst
Low
Outlet of HTS
and LTS
CO Leakage
Srengthening of
the connection
equipment
Medium
Enviromental
risk/Gas
poisoning
45
4.4.ABSORBER
When column diameter is 0.5m<d<1.5m , packed material diameter must be high for not
clogging in column,for this reason packed material diameter was choosen 4 mm. Raching
rings are using at low capacity plants. Raching rings are cheaper than Pall Rings but
efficiency is lower than Pall Rings so column is more expensive for using Raching
rings.Consideration of this conditions , Pall Rings was choosen.
Feed=11.497 tmol/h
XCO=0.0012
XCO2=0.282
XH2=0.686
6.524 tmol/h
XCH4=0.0255
XCO2=0.286
XH2O=0.00113
Absorbe
r
8.253 tmol/h
XCO=0.00156
nlet MEA%20
XH2=0.957
3.28 tmol/h
XCH4=0.0355
XCO2=0.004
XH2O=0.0035
46
Design Basis:
Pin/Tin (Gas):
Pin/Tin (MEA):
Seperation Degree:
Operational Type:
Contact Type:
Column Type:
Packing Material:
H/D ratio for Packed bed column:
Flooding point:
15 bar/40 C
1 bar/ 80C
%99
Adiabatic
Counter current
Packed Bed Column
50 mmmetal pall rings(50-200 mm)
3-5
0.7
4.4.1.Calculations
For NOG :
y1=0.286 (CO2 inlet)
x1=0.282 (CO2 in MEA outlet)
y
y1
L ' x
x

S 1 x 1 x1
1 y 1 y1
V ' V1 (1 y1 )
V'
S
V=11.497 tmol/h
V=11.497(1-0.286)=8.21 tmol/h
L=3.28 tmol/h
y=Ha*x
Ha=Henrys constatt=0.087
y=0.087*x
47
y y y y
y
ln y y y y
*
1
*
1
LM
Y1*=0.022
y y
*
LM
0.038
N OG
y1 y2
y y*
4.44
LM
transfer units
Diameter calculate :
L g
x
V
L
L:3.28 tmol/h
V=11.497 tmol/h=2578.5 ton/h
g
=1.157 kg/m3 (1 atm,40 C)
L
=998.1 kg/m3
L g
x
V
L
=0.402
Material= Metal pall rings
Size=50 mm
Area =92 m2/m3
Void space =78
48
G p2 x 22 x 0.0010.1 x1
1.157 x (998 1.157)
0.08
Gp
=1.57 kg/m2s
Mgas=30.504 kg/kmol
VF
GF
0.052
mgas
tmol/m2s
For %70 flooding head

tmol
1h
m2 s
1
11.497
x
x
x
h
3600s 0.052tmol 0.7
S=0.66 m2
0.66m 2
xd 2
d 0.91m
4
Height of Packing Calculation:

0.7
VM
M V
RT
x
KS

a DV
axM V V xD
V
kg
1/3
axd P
2.0
KS=5.23 for packing size above 15 mm

DV=8x10-9 m2/s,gas dif.
A=92 m2/m3,actual area of packing
DP=packing size =76 mm
VW=gas mass flowrate =0.052 ton/m2s
2.77 x105 kg / ms
kG=0.086x10-3
49
Limit of kG=0.03x10-3-2x10-3
kG PA1 PA 2 kY
y A1 y A 2
kG PT y A1 y A 2 kY y A1 y A 2
k y kG xPT 0.86 x103 kmol / m2 sPa (101.25Pa )
k y 0.00862kmol / m 2 s
1
1
m
x
K y a k y a kxa
K y a k y a K y a 0.00862 x92 0.293
HOG :
V
1
V
V
H OG
K y aS (1 y ) LM
2 K y aS (1 y ) LM
K y aS (1 y ) LM

TOP
HOG=2.168 m
Packed Column Height :
z N OG xH OG 2.168 x 4.44 10.02 10 m

Mechanical Design of Absorber:
Pi xDi
2 f Pi
design pressure ia taken 5 percent
1 atm=1.01 bar
1.01x1.05=1.05 bar=0.105 N/nm2
Design temperature =40 C Design stress =130 N/m2

50
BOTTOM
0.106 x3 x103
1.22mm
2 x130 0.106
Corrosion allowance=2
2+1.22=3.22 mm thickness
CO2 ABSORBER SPECIFICATION SHEET

Item no
T-2
Function
Removing CO2 in gas stream
Operating
Packed Tower
Type
Pall Rings Metallic Packed Material, d=4mm
Operating Pressure
1 bar
Operating Temperature
500C
Total Gas Flow rate (inlet)
11.497 tmol/h
CO2 Flow rate in gas stream (inlet)
3.29 tmol/h
Total Gas Flow rate (outlet)
8.241 tmol/h
CO2 Flow rate in gas stream

(outlet)
3.25 tmol/h
Max. CO2 composition in utility

(MEA)
0.6
Head material
Stainlees steel
Inlet
outlet
H2O
0.112
0.35
H2
68.6
95.7
CO
0.112
0.156
51
C02
28.6
0.4
CH4
2.55
3.55
Column Diameter
0.9 m
Height of column
10 m
Utility
MEA (monoethanolamine)
Total purchased cost (including

installation and auxiliaries
147000 $
Table 12. Risks of Absorber

Where
Risk Type
Cause of Risk
Precaution of
Risk
Cost
In absorber
column
Operational
flexbility
Process control
equipment
Medium
Outlet of
absorber
column
Enviromental
risk
mea failure to
achieve the
temperatures
required for
resolution
Dispending of
CO2
Compact of
connection
equipment
Medium
52
4.5.METHANATION
For occuring low reactor volume , reactor type was choosen. In chemical technologic
books, tubular reactor is suitable for our operational conditions but after our
calculations,tube length was found 20.9 m so decided to use multitubular reactor. One
tube length is setted 3 m with respect to Rule Of Thumbs.
Design Bass For Methanation
Reactor Type
Catalytic Tubular Reactor
Reactor Operation Type
Isothermal
Reactions Conversions
CH 4 H 2O
CO 3H 2
Xa = 0.7
CO H 2O
CO2 H 2
Xb = 0.4
Catalyst
NiO
Catalyst Density, Porosity
Density = 1000 kg/ m3

Porosity = 0.5
Feed Ratio (H2O/CH4)
Flow Rate: 8.241 tmol/h
53
RTotal reaction
P P
k
1
PCH 4 PH 2O H 2 CO 2 2
3,5
PH 2
Ke
Qr
Qr 1 KCO PCO K H 2 PH 2 KCH 4 PCH 4
koj kj (1) e Ej / RT (1)
K H 2O PH 2O
PH 2
, koj (mol/kgcats) = 2,14 109 bar 0,5 , Ej (j/mol)= 211500
Ki = Koi e_Hi/RT
Koi-CH4 (bar-1)= 1,995 10-3
Koi-CO (bar-1)= 8,11 10-5
Koi- H2 (bar-1)= 7,05 10-9
Koi- H2O (bar-1)= 1,68 104 bar
H CH4((j/mol)) = -36650
H CO((j/mol)) = -70230
H H2((j/mol)) = -82550
H H2O((j/mol)) = 8577
8.241 tmol/h
CH4
0.0355
CO2
0.004
STEAM
METHANE
REFORMER
CH4
CO2
54
0.0401
-
CO
0.00156
H2
0.957
CO
H2
0.936
H2O 0.0239
Reactions in Steam Methane Reformer
CH 4 H 2O
CO H 2O
CO 3H 2
CO2 H 2
kj
mole
kj
41,15
mole
1atm
H 25
206
0
C
1atm
H 25
0
C
CH 4 2 H 2O
CO2 4 H 2
1atm
H 25
165
0
C
55
kj
mole
-1/ra - Xa
-1/ra
0.1
0.2
0.3
0.4
Xa
Graph 9. -1/ra XA of steam Methane Reformer
Volume : 4.3 m3
Reactor Szng
Restriction
Dp
0,1
D
h
100
Dp
( P ) B
=3000 Pa/m
Dp = 3 mm
= 3.44 10-5 Pas

= 4.5708 kg/m3
= 0.5
56
0.5
0.6
0.7
0.8
ID = 0.51 m
H = 20.9 m
Calculaton Of Catalyst Amount

Catalyst amount (1 ) xV
kg
x(1 0,5) x4,3m3
3
m
Catalyst amount 2150kg catalyst
Catalyst amount 1000
METHANATOR SPECIFICATION SHEET

Item no
R-4
Function
reaction of carbon monoxide on the catalyst
Operating
Continuous, isothermal
Type
Single bed tubular plug flow
8.241 tmol/h
57
10.6176 tmol/h
Pressure
14 bar
Temperature
295-3100C
Head material
Stainless steel
CO(g) + 3H2(g) > CH4(g) + 3H2O (g)
Reaction
Conversion of CO
0,99
Rh (5%Rh/CeO2 (5%)SiO2) 0,245 void frac., 12.4 g/m3 density
Catalyst type
Component composition %
inlet
outlet
Negligible
2.39
H2
95.7
93.6
CO
0.156
Negligible
C02
0.4
Negligible
CH4
3.55
4.01
H2O
Reactor Size
V=0.78 m3 : ID=0.51m
Htotal=20.9m :
Utility
***
Catalyst cost
***
Total reactor purchased cost 2005
22512$
Installation factor (% ? of
Purchased cost)
0.5
Installed cost
11256 $
H(one tube)=3m
4.6. DISTILLATION COLUMN
Design Basis ;
Condenser
D= 5.63 tmol/h
B= 2.33 tmol/h
XNH3 =0.0088
F= 7.967
tmol/h
XNH3 = 0.29
Distillation
Column
XNH3 = 0.978
XN2=0.246
L0
58
XN2=0.53
XH2= 0.17
Reboiler
XN2=0.0175
XH2= 0.74
XH2= 0.00605
Key components ;
Heavy Key: Ammonia Light Key :Hydrogen
Degrees Of Freedom For Distillation Column ;
Feed Flow
=1
Bottom Flow
=1
Reflux
=1
The Composition Of The Bottom Component
=1
Column Pressure
=1
Condenser Or Reboiler Duties
=1
The Feed Tray Location
=1
Total Number Of Trays
=1
Total
=8
Selected Variables
The Composition Of Formaldehyde Component in Recycle
=1
Recycled Stream Pressure
=1
Reflux Ratio
=1
Known Equations [ F= D+B and R= (refluxratio) Rmin]
=2
Known Variables
Feed Composition
=1
59
The Composition Of Methanol Component
=1
Product Flow
=1
Degrees Of Fredom
8-8=0
Material Balance:
F=D+B
7.967 tmol/h = 5.63 tmol/h +B
B = 2.33 tmol/h
Ammonia Balance;
7.967* 0.29 = 2.33 *XB + 5.63 * 0,0088

xB,Ammonia = 0,978
Hydrogen Balance;
7.967* 0.53 = 2.33 * 0,0175 + 5.63 * xD,hydrogen

xD,methanol = 0,74
Nydrogen Balance;
7.967 * 0.17 = 0,0141* 0.00605 + 5.63 * xD,Nydrogen

xDNydrogen = 0.246
Design Basis :
Distillation Type:
Hydrogen recovery =% 99,9
Nydrogen recovery = % 99,95
Feed Conditions: 1,3atm, 75 C
Continuous
Heavy Key = Ammonia
Light Key = Hydrogen
Composition: Hydrogen
60
= 0,53
Feed Flow Rate: 7.917 tmol/h

Phase: Saturated Liquid
Nydrogen
= 0,17
Ammonia
= 0,29
Compositions: Hydrogen = 0.74
Top Conditions: 1,15atm, 68 C

Top Flow Rate: 5.63 tmol/s
Nydrogen= 0,246
Phase: Gas
Bottom Conditions: 1,34 atm, 78 C
Ammonia = 0,0088
Composition: Hydrogen = 0.0175
Bottom Flow Rate: 2.33 tmol/s
Nydrogen= 0,00605
Phase: Liquid
Condenser Utility: Water
Ammonia = 0,978
Reboiler Utility: Saturated Steam
Tin : 30 oC Tout :55 oC
Tin : 150 oC Tout : 150 oC
Pressure :1 atm
Pressure : 4atm
Condenser Type: Partial
Reboiler Type: Partial
Column Settings:
value must be equal to 1.0
Ki values for methanol is taken from

references App[A3].
Trial and error is done and Ttop is found as
341 K (68 oC).
Table 14.Temperature Calculation Of Feed Stream
348 K
Hydroge 1,00399
n
5
1
Xi
i*xi
Yi =
Xi*Ki
yi/
0,0481
0,04836 0,04836
7
0,04817 2
2
Nydroge 0,26696 0,26590

0,16342 0,16407 0,61705
n
7
4
0,6146 5
8
6
Ammoni 12,6979 12,6473
4,26469 4,28173 0,33854
a
1
8
0,3372 6
5
7
61
1,00396
5
0,99605
Table 15.Temperature Calculation Of Bottom
352 K
xi
yi
*yi
Hydrogen
1,13292
9
3,84422
5
0,00044
3
0,00050
1
0,001701
Nydrogen
0,29470
9
0,64312
7
0,18953
6
0,643127
Ammonia
13,2122
8
44,8315
7
0,35649
4
4,71009
9
15,98219
16,62701
0,982673
Table 16.Temperature Calculation Of Top
341 K
Hydrogen
0,99042997
7
1
Xi
yi
0,8856
0,87712 0,87712
5
5
0,8856
62
yi/
x*
Nydrogen
0,24359001 0,24594
7
4
0,114
0,02776 0,11290
9
9
Ammonia
13,6503473 13,7822
4
4
0,0004
0,00039 0,00551
0,00546 6
3
0,99043
1,00966
2
value of light key at dew point tempreture.
value of light key at buble point tempreture.
= 1,97
Nmin =
Nmin =
= 17,78
Nmin = 17,78
= 1-q
18stages
; q=1 for feed at the boiling point.
63
0,02803
8
= 2,194
Column Efficiency : % 80
= 0,75 [ 1-
= 1,4
=3,1813
= 0,75 [ 1-
N = 19,80
20 (N theoretical)
= 24,75 25 (N actual)
Nr = number of stages above the feed, including any partial condenser,

64
Ns = number of stages below the feed, including the reboiler,

B = molar flow bottom product,
D = molar flow top product,
xF,HK = Concentration of the heavy key in the feed,
xF,LK = Concentration of the light key in the feed,
xD,HK = Concentration of the heavy concentration of the heavy key in the feed,
= 0,1274
Nr= Ns*0,1274
Nr + Ns =25
0,1274Ns + Ns = 25
Ns= 22,17 23 (Top)
Nr =2 (Bottom)
Calculation Pressure Drop:
Ptop = PFeed -0,0074*23 ; Ptop= 1,13atm
PFeed = 1,30atm
Pbottom = (0,0074*2) + 1,30 = 1,32 atm
Calculation Of Column Diameter:

65
mmix=0,29*17 + 0,53*2 + 0,17*28 = 9.22 kg/kmol

At Dew Point:
1,1 atm ; 68,11 oC
Nydrogen
(68,11 oC ) = 0.071 kg/
Ammonia
(68,11 oC ; 1,1 atm) = 0.6122 kg/
Hydrogen
(68,11 oC ; 1,1 atm) = 0.071 kg/
= 0.071*0.246 + 0.6122*0.0088 + 0,071*0.74
= 0.,075 kg/
=R
= 3,1813 * 5.63 = 17.9 tmol/h
+D
= 17.9 + 5.63 = 23.5 tmol/h
+F
66
= 17.9 + 7.967 = 25.86 tmol/h
-B
= 25.862.33= 23.53 tmol/h
P*
* R*T
1,13 * 9.22 =
* 0,0082 * (68,11+273,14)
= 3.72 g/L
25.86
23.53
3.72
9.22
*
= 0,69
Assume tray spacing : 0,61

= 0,065
= 0,065*
9.22 3.72
3.72
0.5
67
= 0.0806 m/s
Assume % 80 flooding, 1 for fooming (18)

= 0,8 * 0.0806 = 0.064 m/s
Volumetric flow rate at vapor phase;

Ammonia = % 0,05 = 0,0004
Nydrogen = % 0.246 = 0,114
Hydrogen = % 0.74 = 0,8856
mAmmonia = 30,026 g/mol
mNydrogen = 18,01508 g/mol
mHydrogen = 32,04 g/mol
mmixer = 0,0004*(30,026) + 0,126 *(18,01508)+ 0,87 *(32,04)
mmixer = 30,16 g/mol
8,4 kmol/h *
= 0,070 kg/s
= 0,057
= 0,482
D = 0,784 m
68
4.6.1.Height Of Column Calculation

Assumptions;
The space above the column is 1,5 times the tray spacing
The space below the column is 1.5 times the tray spacing
Extra height for the feed tray is 0,25 times the tray spacing
Tray spacing is chosen as 0,61
HT = 1,5 *IR + (N-1)*IR + 0,25*IR + 1,5*IR

HT = (3,25 + (N-1))*IR
HT = (3,25 +(N-1))*0,61
HT = (3,25 +(25-1))*0,61
HT = 16,62 17 m (10% free volume is applied to the height of the column for pressure
control.)
4.6.2.Calculation of wall thickness

Stainless steel is chosen as material of construction.
Pfeed = 1,30*1,1 = 1,43
% 10 safety factor addition ;
tmin =
t = wall thickness
S = maximum allowable working stress Kp
Ej = Efficiency of joinst expressed as a fraction
S = 128900 kPa for stainless steel 316
Ej = 0,75
Corrosion factor is 0,00016
69
Minimum wall thickness:

=
+ 0,00016
= 7,40 *10-4 m
+ (% 10 safety )*
= 8,14*10-4m
Table 17. Specification Sheet Of Distillation Column

Function
Seperation for Hydrogen and Nydrogen from

Ammonia
Type
Continuous
Fluid handle
F=7.967 tmol/h
XNH3 = 0,258
XN2=0,037
XH2= 0,705
Temperature (oC)
75
Pressure (atm)
1,3
Reflux ratio, RD /RDmin
1,4
Actual number of trays
25
Diameter,m
0,8
70
Height,m
17
Material of Construction
Stainless Steel 316
Cost,$
145500
Table 18. Risks of Distillation Column

Where
Risk Type
Cause of Risk
Precaution of
Risk
Cost
Dew section
Operational
flexbility
Purchased
dedector
Medium
Bottom section
Operational
flexbility
Increasing the
Wall thickness.
Medium
Feeding and
outside of
columns
Operational
flexbility
From the top to

intensify the
light gases at
high pressure
using control
equipments at
condenser;
leaking of these
equipments
interaction.
Evaporated
from the bottom
of the product
for the high
pressure
Leaking of
distillation
column and
feeding, sources
of static
electricity due
to the proximity
of the column.
Purchased
dedector
Medium
71
4.7. AUXILARY EQUIPMENTS
Heat Exchanger (E-1)
Design basis
Steam
0.896
tmol/h
Syn
Gas
8.917
tmol/h
Syn
Gas
Steam
0.896
tmol/h
72
3000C,10
11.49
tmol/h
Assumed=20W/m2C
Tube diameter:0,0154m
Lenght =2m square pitch=1,25 1-1shell and tube
After Chemcad calculation:

Tout:2000C
Area : 24.2 m2
Area of per tube=xODxL=x0,0254x2=0,16m2
Number of tubes=24,2/0,16=152tubes
Standart of tubes =177 tubes
App 21
14tubes
Widht=14
tubesx0,0254x1,25=0,44m
13tubes
High=13 tubesx0,0254x1,25=0,41m
73
P.Cost = 9x104$
Design basis
Cooling Water
Nwater=?
72 C,1 atm
Syn Gas
(HTS outlet)
Syn
Gas
11.49
tmol/h
11.49 tmol/h
18atm
18atm
Cooling Water
Nwater
280C,1 atm
Assumed=20W/m2C

Nwater=2.579 tmol/h
Area : 73.85 m2
74
25tubes
Widht=25 tubesx0,0254x1,25=0,79m
24tubes
High t=24 tubesx0,0254x1,25=0,76m
P.Cost= 12x103$
Design basis
Cooling water
2.579 tmol/h
10 atm
75
Syn Gas(LTS
outlet)
11.49 tmol/h
Syn Gas
Cooling
water
11.49 tmol/h
2.579tmol/h
Assumed=75W/m2C App22

Tout=69 C
Area : 35,5 m2
25tubes
76
Widht=25tubesx0,0254x1,25=0,79m
24tubes
High =24 tubesx0,0254x1,25=0,76m
P.Cost= 6x103$
Design basis
Steam
0.896 tmol/h
10atm
Process
stream(Absorbe
r outlet)
Process
stream
8.241 tmol/h
8.241 tmol/h
50 C,13 atm
Steam
0.896 tmol/h
Assumed=75W/m2C

77
Tout=193C
Area : 11,27 m2
14tubes
13tubes
High =13 tubesx0,0254x1,25=0,41m
P.Cost= 3 x103$
Absorbtion
outlet stream
0.896 tmol/h
Design basis
10 atm
Tout=?
78
Process
stream(Outlet
Meth.)
Process stream
8.04 tmol/h
350 C,13 atm
8.04 tmol/h
3100C,13 atm
Steam
0.896 tmol/h
300 C . 10atm
Assumed=75W/m2C

Tout=290 C
Area : 11,27 m2
14tubes
79
13tubes
High =13 tubesx0,0254x1,25=0,41m
P.Cost2002= 5 x104$
App23
Design basis
Steam
0.896 tmol/h
10atm
N2 from Air
seperation
24mol/s
500C,3 atm
Process stream
Steam
24mol/s
0.896 tmol/h
350 C,3 atm
300 C , 10atm
Assumed=75W/m2C App22
80

Tout=130C
Area : 11,27 m2
14tubes
13tubes
High =13 tubesx0,0254x1,25=0,41m
P.Cost= 3x103$
Compressor(C-1)
Operation Type = Adiabatic
C-1
81
11 atm
22 atm
8.917 tmol/h
8.917 tmol/h
H2= 0.57
H2= 0.57
CO=0.29
CO=0.29
CO2=0.107
CO2=0.107
CH4=0.033
CH4=0.033
T2 P2

T1 P1
T2 22

28 11
=1.22
0,22
1.22
T2
=32 C
P
P1 V1
1 2
1
P1
1.22 1
1.22 11 2
22 1.22
1.22 1
11
=-16.24 kw
Expander(C-2)
C-2
16 atm
11.497 tmol/h
H2= 0.686
CO=0.00112
CO2=0.286
CH4=0.0255
1 atm
11.497 tmol/h
H2= 0.686
CO=0.00112
CO2=0.286
CH4=0.0255
82
H2O=0,0112
H2O=0,0112
T2 P2

T1 P1
T2 1

260 16
=1.22
0,22
1.22
T2
P1 V1
=160 C
1
P2
1
P1
1.22 1
1.22 16 23
1 1.22
1.22 1
16
=+80.2 kw
Expander(C-3)
C-3
16 atm
11.497 tmol/h
H2= 0.957
CO=0.00156
CO2=0.004
CH4=0.0355
H2O=0,0035
1 atm
11.497 tmol/h
H2= 0.957
CO=0.00156
CO2=0.004
CH4=0.0355
H2O=0,0035
83
T2 P2

T1 P1
=1.22
0,22
1.22
T2 13

50 1
T2
=80 C
P2
P1 V1
1
P1
1.22 1
1.22 1 3.4
13
1.22
1.22 1
1
=-11.0 kw
Kademeli Sktrma
r
P
P2 P3 P4
... k
P1 P2 P3
Pk 1
150 100 66 44 29 19.5
100 66 44 29 19.5 13
Pk
P1
150
13
=6 pressure ratio
=2 kademe
Compressor (C-4)(C-5)
C-4
C-5
13 atm
66 atm
8.241tmol/h
8.241tmol/h
8.241tmol/h
H2= 0.936
H2= 0.936
H2= 0.936
CH4=0.0401
H2O=0,0239
150 atm
CH4=0.0401
H2O=0,0239
84
CH4=0.0401
H2O=0,0239
For C-4 Compressor
T2 P2

T1 P1
=1.22
T2 66

310 13
0,22
1.22
T2
P1 V1
=415 C
1
P2
1
P1
1.22 1
1.22 13 1.62
66 1.22
1.22 1
13
=-39.75 kw
For C-5 compressor

T2 P2

T1 P1
T2 13

50 1
=1.22
0,22
1.22
T2
=481 C
P2
P1 V1
1
P1
1.22 1
1.22 66 0.42
150 1.22
1.22 1
66
85
=-24.5 kw
Table 19. Risks of Heat Exchanger

Where
Risk Type
Cause of Risk
Precaution of
Risk
Cost
Shell side
Operational
safety
Increasing the
Wall thickness
and purchased
dedector.
High
Inlet and outlet

of heat
exchangers
Operational
safety
Because of
increasing the
temperature and
pressure may be
occur leaking at
shell so contact
with hot surface
and temperature
controllers.
Come into
contact with
sparks may be
occurring while
heat exchanger
contact with hot
surface and
temperature
controllers,
while leaking.
Purchased
dedector.
Medium
Table 20. Risks of Compressor

Where
Risk Type
Cause of
Risk
Precaution of
Risk
Cost
Inlet and outlet

of compressors
Operational
safety
Leaking at
connection
parts due to
increasing
Compact of
connection
equipment.
Medium
86
the pressure;
may be
occur
damage at
mechanical
parts of
compressors
.
Table 21. Main Equipment Cost Analysis

Equipment
Material of
Service
Lenght
Purchased
Name
Construction
Life
or Area
Cost
(year)
or
Utility
Utility
Total
Cost
Cost
(TL/yr)
Volume
or
Power
(m/ m2
/m3
/kW)
Storage Tank
316 stainless
(Raw Material)
steel
10
243000
341720
5879 m2
Storage Tank
316 stainless
(Product)
steel
Reactor
Carbon steel
10
321 m2
21156
29910
10
3.64-
193268 $
catalyst
19344.6
483170
2.04-
2.46 m3
Absorption
316 stainless
Column
steel
10
H = 10
m
D = 0,9
m
87
58800
Water
10075
147000
$
Dstillation
316 stainless
Column
steel
10
H = 17
m
D=
0,8m
88
58200
145500$
5.RESULTS AND DISCUSSION

In this report, a plant is designed for which is desired to produce max 1400 ton/year 99%
ammonia from air and synthesis gas by Haber Bosch Medium Pressure Process, in
Sinop/TURKEY.
According to this aim detailed design of main and auxilary equipments are done, cost items
are discussed and cost of each equipments are calculated. By looking the reactor inlet and
working conditions; first feed preperation part is designed and it is started with raw material
storage tank..When designing this tank Sinops summer temperature conditions are thought
and design temperature is setted as 30 oC. According to 3 hours residence time and
calculations, it is found 11 m diameter and 5879 m3 volume and uses 11 tank . Stainless steel
is used as material of construction with a 0.13 m thickness. So according to the values cost
was calculated as 341720 $.
Another main equipment-reactor is designed according to the reaction temperature, catalyst
decomposition temperature (limiting temperature), conversion and volume of the tank. As it
was pointed out in the report before inlet conditions of the reactor are 350oC, 150 atm. The
temperature which is need to react the mixture is 400-500oC range so this is supplied by the
help of burning H2 with O2. Also because of the reaction is exothermic,reaction takes place on
its own. The reactor has a volume of 8 m3 .Conversion of the reactor is calculated as 0.45 by
looking the material of construction, bed volume and catalyst cost of the reactor is 254365 $.
To absorp carbondioxide into the MEA(monoetanolamine) and seperate from the gas stream
packed tower absorption column was used. MEA is used as solvent and it is fed to the column
at 80 oC from top of the column.. To determine the operating pressure of the column
equilibrium curves are researched and 40 oC, 15 bar, equilibrium data is used. Column works
isobaric and adiabatic. 50mm metal pall rings is used as packing material and height of the
column is 0.91 m and diameter of column is 10 m. After the ammonia reactor, tray tower
distillation column is used to seperate hydrogen from ammonia solution.In this column
solution is fed at 75 oC, 1.3 atm as saturated liquid and ammonia setted as heavy key and
hydrogen selected as light key. According to these calculations diameter of column is 0.8m,
height of column is 17 m..So cost of this equipment is 147000$.
After cooling the bottom stream of distillation column to -33 C it is stored at ammonia storage
tank. This tank is closed to the atmosphere and has a diameter of 7.4 m, 8.8 m height and 321
89
m3 volume and use 4 tank which is constructed from (material cons) with a 0.063 cm
thickness.Cost of this tank is 29910 $.
As it is pointed out before each of the main equipments have in and out conditions and to
supply these conditions some other equipments used like heat exchangers,compressor and
expander. First heat exchanger E-1 is used to heat the syn gas from 28 C to 150 C. To supply
the technical ability and operational flexibility it is designed according to the winter weather
conditions min temperature average which is 66 C. This heat exchanger uses super heated
steam as utility. Another cooler E-2 is used to cool the syn gas from 420 C to 200 C which
uses cooling water utility.. So it is the main cost item fort his equipment.To decrease pressure
which uses in LTS outlet expander (C-2) is used. In this equipment electricity used as
utility.In this equipment pressure also decrease to 1 atm before the mixture goes into CO2
removal (A-1). E-3 is used after absorber to heat the outlet stream 80 C
6 to 200 C
6 to supply
saturated liquid condition.This heat exchanger is used saturated stream as utility.
As a conclusion process is designed equipment by equipment and cost items of each are
discussed and all of them priced.In this report calculated costs includes also precautions to
risk factors. So in the next report it will be again examined to have a final pricing and plant
location by the help of these determined specifications.
90
6. REFERENCES
1. PETERS,M.S., TIMMERHAUS,K.D. WEST,R.E. Plant Desing and Economics for
Chemical Engineers ,fifth edition , The McGraw-Hill Companies ,inc., page 60-61,2002.
2. SINNOT,R.K., Chemical Engineering Design: Principles, Practice and Economics of Plant
and Process Design.
3. http://www.mgm.gov.tr/tahmin/il-ve-ilceler.aspx?m=SINOP
4. BRANAN, C.R. Rules of Thumb for Chemical Engineers, (2002).
5. Kirk-Othmer Encyclopedia of Chemical Technology.
6. [Rule of thumb page 250]
7. Geankoplis, C.,J., Transport Processes and Seperation Process Principles, 4 th Edition,
Prentice Hall, New Jersey, 2003(p.71,72,91-101,139,144).
8. W.D. Seider, J. D. J. D. Seader and D. R. Lewin, Procees Design Principles:Synthesis,
Analysis and Evaluation, Wiley and Sons ,New York, 1999,page 141-154.
9. B. Zht Uysal Ktle Aktarm,
91
APPENDIX
Appendx 1
Appendx 2
Table A.1 Cost tabulation for selected utilities and labor
92
Appendx 3
Figure A.1 Purchased cost of fixed-tube-sheet heat exchangers [1]
Appendx 4
Figure A.2 Purchased cost of Reboiler
93
Appendx 5
Figure A.4 Distillation and absorption column purchased cost
Appendx 6
MSDS of substances
Components
Fire
fighting
measures
Physica
l and
chemic
al
propert
ies
Chemical
Stability,
reactivity
Environ
-
Flammable
limits :
12.5-74.2%
Melting
point:
Autoignition:60
-205.15
C
-
Very
flammable
and
toxic.Read
ily forms
explosive
mixtures
with air.
Vaporize
d matter
its
emission
s
benings
to
environ
1. CO
94
Toxicol
ogy
Mental
CO gas
is
irritatin
g to
breathin
g and
eyes.
5C
Boiling
point:
ment
-191.7
C
Density
at 0 C
1.250k
g/m3
2.
Hydrog
en
Flammable
limits:474%
Autoignition:56
5.5CBurns with
a pale blue,
nearly
invisible
flame.
-Hydrogen
is easily
ignited with
lowignition
energy,
including
static
electricity.
Colorles
s gas at
normal
tempera
ture and
pressure
.
molecul
ar
weight:
2.016g
Hazardous
decompos
ton
products:
none
Hazardous
polymerz
aton will
not occur.
specfc
gravity
(air =1)
0.06960
gas
densty
at 21.1o
C and 1
atm):
0.08342
kg/m3
-Hydrogen
is lighter
than air and
can
accumulate solublt
in the upper y n
95
- No
adverse
ecologic
al
effects
are
expected
.
Hydrog
en is a
simple
asphyxi
ant.
3.
Methan
e
sections of
enclosed
spaces
water
(vol/vol
at 15.60
c):
0.019
- Methane
is slightly
heavier
than air and
may travel
a
considerabl
e distance
to an
ignition
source.
Should
flame be
extinguishe
d and flow
of gas
continue,
increase
ventilation
to prevent
flammable
mixture
formation
in low
areas or
pockets.
Boiling
Point:
161.4C
Methan
e is
inactive
biologic
ally and
essentia
lly
nontoxi
c;
therefor
e, the
majority
is the
exclusio
n of an
adequat
e supply
of
oxygen
to the
lungs.
-stable
-Liquid
Density
at
Boiling
Point:
424.5
kg/m3
-Gas
Density
at 1 atm
0.0052
96
5. CO2
Nonflamma ble.
Boiling
Point:
-56,6C
-stable
Moderat
ely
irritatin
g to
eyes.
Moderat
ely
irritatin
g to the
skin.
Density
at 0
C&1at
m:
1.977 k
g/m3
6.Amm
onia
Flammable
limits:1625%
Autoignition:65
1C
Moderat
ely
irritatin
g to the
respirat
ory
system.
Molecul
ar
weight
17
-stable
-Boiling
point
-33C
Melting
point
-78C
Exposur
e to
Ammon
ia can
cause
moderat
e to
severe
eye
irritatio
n
Ingestio
n is not
a likely
route of
exposur
e for
Ammon
ia
Vapor
97
contact
may
cause
irritatio
n and
burns
98

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1.

2. FLOWSHEET THAT TO BE DESIGNED

Figure 1. Flowsheet that to be designed

Flow Diagram of Overall System for Ammonia Process

Unknowns : 6 (nH2, nN2, nCH4, nH2O, nCO, nCO2) (+)

Chemical reaction : 2(+)

Eqns relating unknown variables: 2 (-)

Water 2.58 tmole/h

MEDIUM PRESSURE PROCESS

CH4 3.030 tmol/h

Table 2. Molecular Spieces Balance Equations

Table3. Input And Output Streams

Input Stream Flowrate(tonmole/h)

Output Stream Flowrate(tonmole/h)

3.3. Material Balance for Each Equipment

%99 CO2 get absorbed

3.3.3. Material Balance for Distillation Column

7.967* 0.29 = 2.33 *XB + 5.63 * 0,0088

7.967* 0.53 = 2.33 * 0,0175 + 5.63 * xD,hydrogen

7.967 * 0.17 = 0,0141* 0.00605 + 5.63 * xD,Nydrogen

Table 4. Stream Summary Table

Air Seperation inlet

CO2 Removal inlet

CO2 Removal outlet

Why stainless steel material ?

No need for long time storage

Why 12 hours ammonia residence time?

No need for long time storage

Factory close to market

Why closed tank for synthesis gas storage ?

Methane is volatile and easily flammable

Dead Volume Reason

Particles from the tank due to corrosiveness of methane or ammonia.

Size of storage tank (raw material storage)

tmol 1000kmol 14.96kg

Total volume of the tank:

Surface area of tank:

Thickness of Storage Tank

Ej: efficiency of joints expressed as a fraction

Total cost of tank = cost of material + cost of painting + cost of installation

4.1.2.2.Sample Calculations for Ammonia Storage Tank

Design Basis of Storage Tank

Size of storage tank (product storage)

ton 1000kg 1day

Thickness of Storage Tank

Ej: efficiency of joints expressed as a fraction

Total cost of tank = cost of material + cost of painting + cost of installation

= 21156 + 292 +8462.4 = 29910

Size of the Tank:

Table 5. Risks of Storage Tanks

Table 6. Specification Sheet of Raw and Product Material Storage Tank

Item: Syntesis Gas Storage Tank

Item:Ammonia Storage Tank

Function: Raw Material Storage

Function: Product Material Storage

Composition: 57% H2,29%CO,10.7%CO2, Composition: 99.9% NH3

atm (1+safety factor)

Number of storage <12[4]

4.2.REACTOR (AMMONIA CONVERTER)

150 bar - 425C

Design Basis 2nd Reactor

150 bar - 300C

Design Basis 3rd Reactor

7.967* 0.29 = 2.33 XB + 5.63 0,0088