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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:
Toperating < 500 C (for nonactive of
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:
Toperating < 500 C (for nonactive of
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

Continous, adiabatic
Kinetic reactor, Multi-Tubular Reactor

Type

Low temperature shift

Total Flow rate (inlet)

11.49 tmol/h

Total Flow rate (outlet)

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

Component composition % mol

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

Continous, adiabatic
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

Component composition % mol

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

Total Flow rate (inlet)

8.241 tmol/h

57

Total Flow rate (outlet)

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$

Heat Exchanger (E-2)

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
Tube diameter:0,0154m
Lenght =2m square pitch=1,25 1-1shell and tube

After Chemcad calculation:


Nwater=2.579 tmol/h
Area : 73.85 m2
Area of per tube=xODxL=x0,0154x2=0,12m2

74

Number of tubes=73,85/0,12=501tubes

25tubes

Widht=25 tubesx0,0254x1,25=0,79m

24tubes

High t=24 tubesx0,0254x1,25=0,76m

P.Cost= 12x103$

Heat Exchanger (E-3)

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
Tube diameter:0,0154m
Lenght =2m square pitch=1,25 1-1shell and tube

After Chemcad calculation:


Tout=69 C
Area : 35,5 m2
Area of per tube=xODxL=x0,0154x2=0,12m2
Number of tubes=73,85/0,12=501tubes
Standart of tubes =590 tubes

25tubes

76

Widht=25tubesx0,0254x1,25=0,79m

24tubes

High =24 tubesx0,0254x1,25=0,76m

P.Cost= 6x103$

Heat Exchanger (E-4)

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
Tube diameter:0,0154m
Lenght =1m square pitch=1,25 1-1shell and tube

After Chemcad calculation:


77

Tout=193C
Area : 11,27 m2
Area of per tube=xODxL=x0,0154x1=0,07m2
Number of tubes=11,27/0,07=158tubes
Standart of tubes =177 tubes

14tubes

Widht=14 tubesx0,0254x1,25=0,44m

13tubes

High =13 tubesx0,0254x1,25=0,41m

P.Cost= 3 x103$

Absorbtion
outlet stream

Heat Exchanger (E-5)

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
Tube diameter:0,0154m
Lenght =1m square pitch=1,25 1-1shell and tube

After Chemcad calculation:


Tout=290 C
Area : 11,27 m2
Area of per tube=xODxL=x0,0154x1=0,07m2
Number of tubes=11,27/0,08=150tubes
Standart of tubes =177 tubes

14tubes

79

Widht=14 tubesx0,0254x1,25=0,44m

13tubes

High =13 tubesx0,0254x1,25=0,41m

P.Cost2002= 5 x104$

App23

Heat Exchanger (E-6)

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
Tube diameter:0,0154m
Lenght =1m square pitch=1,25 1-1shell and tube

80

After Chemcad calculation:


Tout=130C
Area : 11,27 m2
Area of per tube=xODxL=x0,0154x1=0,07m2
Number of tubes=11,27/0,08=150tubes
Standart of tubes =177 tubes

14tubes

Widht=14 tubesx0,0254x1,25=0,44m

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)

Operation Type = Adiabatic

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)

Operation Type = Adiabatic

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)

Operation Type = Adiabatic

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