CHAPTER-1

MATERIAL BALANCE FOR AMMONIA PRODUCTION PLANT

BASIS: 1000 Kmol of (N2-H2) mixture to the ammonia synthesis reactor.

1.1 MATERIAL BALANCE OVER PRIMARY REFORMER:

1.1.1. ASSUMPTIONS:

1. Natural Gas contains 95% methane and 5% ethane.

2. Assuming 100% conversion of ethane and 86% of methane.

1.1.2. COMPOSITIONS:

1. Methane = 3610kg = 225.6 kmol

2. Ethane = 190 kg = 6.3 kmol
P R
3. Natural Gas = 3800 kg CH4
R E
4. Steam = 7000 kg =389 Kmol
I F
CO
M O
STEAM H2O
A R

NATURAL GAS R M H2
Y E

1.1.3. REACTIONS:
CH4+H2O CO + 3H2
C2H6 + 2H2O 2CO +5H2

1
 INPUT OUTPUT
CH4 = 3610kg = 225.6 Kmol CH4 = 31.5Kmol =504 kg

C2H6 = 190kg =6.3 Kmol H2O = 182.3 Kmol = 3281.4 kg

H2O = 7000kg = 389 Kmol CO= 206.6 Kmol =5784.8kg

H2 = 613.5 Kmol = 1227 kg

TOTAL = 10800 kg TOTAL = 10796.8 kg

1.2. MATERIAL BALANCE OVER SECONDARY REFORMER:

1.2.1. ASSUMPTIONS:
SR
70% conversion of reactants Air N2
E E
1.2.2. COMPOSITION: CH4
C F
Ar

N2 = 250 Kmol = 7020 kg H 2O O O H2O

N R
Ar = 2.25 Kmol = 90 kg CO CO
D M

O2 = 59.5 Kmol = 1890 kg H2 A E H2

R R
Air=9000kg CO2 CO2
Y

O2 CH4

1.2.3.REACTION:

CH4 + 2O2 CO2 + 2H2O

Let, X be the amount of CH4 recycled to the reformer.

2
 INPUT OUTPUT
N2 = 250 Kmol = 7020 kg N2 = 250 Kmol = 7020kg
Ar = 2.25 Kmol = 90kg Ar = 2.25 Kmol = 90 kg
O2 = 59.5 Kmol = 1890 kg O2 = 59.5- 14(31.5+10x) Kmol
CH4 = (31.5 + x) Kmol =( 504 + 160x )kg CO = 206.6 Kmol = 5784.8Kg
H2O = 182.3 Kmol = 3281.4 kg H2 = 613.5 Kmol = 1227Kg
CO = 206.6 Kmol = 5784.8 kg CH4 = 3(31.5+10x) Kmol
H2 = 613.5 Kmol = 1227 kg H2O={182.3 +14(31.5+10x)}Kmol
CO2 = 7(31.5+10x) Kmol CO2= 0.7(3.15+X)Kmol

1.3. MATERIAL BALANCE OVER SHIFT CONVERTOR:

1.3.1. ASSUMPTION:

95% conversion of the reactants in the shift reactor.

1.3.2. REACTION:

CO + H2O CO2 + H2

N2 N2
Ar S R Ar
O2 H E O2
CO CO
I A
H2 H2
F C
CH4 CH4
H2O T T H2O
O
CO2 CO2
R

3
 INPUT OUTPUT
N2 = 250 Kmol = 7020 kg N2 = 250 Kmol
Ar = 2.25 Kmol Ar = 2.25 Kmol
O2 = 5.95 - 14( 31.5 + x) Kmol O2 = 59.5 – 14(31.5+x) Kmol
CO = 206.6 Kmol CO = 10.33 Kmol
H2 = 613.5 Kmol H2 = 800 Kmol
CH4 =. 3( 31.5+x) Kmol CH4 = .3(31.5+x) Kmol
H2O = { 182.3 + 14( 31.5 +x)} Kmol H2O = (30.13 + 14x) Kmol
CO2 = .7( 31.5 + x) Kmol CO2 = (218.3 + .7x) Kmol

1.4. MATERIAL BALANCE OVER CO2 SEPARATOR:

1.4.1. ASSUMPTION:95% of CO2 is being removed.

CO2
N2 S
N2
Ar E
Ar
O2 P O2
CO A CO
H2 R H2
H2O A H2O
CH4 T CH4
CO2 O CO2
R

4
 INPUT OUTPUT

N2 = 250 Kmol = 7020 kg N2 N2 = 250 Kmol = 7020 kg

Ar = 2.25 kmol = 90 kg Ar Ar = 2.25 kmol = 90 kg

O2 = 59.5-1.4 (31.5+x) kmol O2 = 59.5-1.4 (31.5+x) kmol

CO = 10.33 kmol = 289.24 kg CO CO = 10.33 kmol = 289.24kg
H2 = 800 kmol = 1600 kg H2 H2 = 800 kmol = 1600 kg

CH4 = 0.3 (31.5+x) kmol CH4 = 0.3(31.5+x) kmol

H2O = (30.13+1.4x) kmol H2O = (30.13+1.4x) kmol
CO2 = (218.32+0.7x) kmol CO2 = 0.05 (218.32+0.7x) kmol

1.5. MATERIAL BALANCE OVER METHANATOR:

1.5.1. ASSUMPTION:Assuming55%conversion in the methanator.

1.5.2. REACTION: CO +3H2 CH4 + H2O

CO2 + 4H2 CH4 +2H2O

M
N2 N2
E
Ar Ar
T
O2 O2
H
H2 H2
A
CH4 N
CH4
H2O A
H2O
CO2 T CO2

5
 INPUT OUTPUT

N2 = 250 kmol = 7020 kg N2 N2 = 250 kmol = 7020 kg

Ar = 2.25 kmol = 90 kg Ar Ar = 2.25 kmol = 90 kg

O2 = 59.5-(31.5+x) kmol O2 = 59.5-(31.5+x) kmol

CO = 10.33 kmol = 289.24 kg CO = 4.64 kmol = 129.92 kg

H2 = 800 kmol = 1600 kg H2H H2= 800-1.65- {2.2*0.05(218.3-0.7x)} kmol
CH4 = 0.3 (31.5+x) kmol CH4=0.3(31.5+x)+5.68+0.0275(218.3+0.7x)
kmol
H2O = (30.13+1.4x) kmol H2O=(30.13+1.4x)+5.68+0.055(218.3+0.7x)
kmol
CO2 = 0.05 (218.3+0.7x) kmol CO2 = 0.0225(218.3+0.7x) kmol

Vent CO2 = 0.95 (218.3+0.7x) kmol

Now, CH4 is recycled,

0.3(31.5+x)+5.68+0.0225(218.3+0.7x) = x

=> x = 28

Therefore, CH4 recycled = 28 kmol = 44.8 kg

Putting the values of x and then making the balance, we get,

6
1.6. MATERIAL BALANCE OVER CO2 SEPARATOR:

1.6.1. ASSUMPTION:95% of the carbon dioxide is being removed.

INPUT OUTPUT

N2 = 250 kmol = 7020kg N2 = 250 kmol = 7020kg

Ar = 2.25 kmol = 90kg Ar = 2.25 kmol = 90kg

CO = 10.32 kmol =289.24kg CO = 10.33 kmol = 289.24kg

H2 = 800 kmol = 1600kg H2 = 800 kmol = 1600 kg

CH4 = (31.5 + 28) = 17.85 kmol = CH4 = 17.85 kmol = 285.6kg

285.6Kg

H2O = 30.13+(1.4*28)= 69.33kmol H2O = 30.13+(1.4*28) kmol= 69.33

kmol=1257.94kg
= 1247.94kg

CO2 = 218.32 +( 0.7*28) CO2 = 11.895 kmol = 523.38 kg

TOTAL = 20999.84Kg TOTAL= 10328.22Kg

95% of CO2 is removed = 226.005

kmol= 9944.22kg

TOTAL= 20999.84Kg

1.7. MATERIAL BALANCE OVER METHANATOR:

1.7.1. ASSUMPTION: 55% conversion in the methanation.

1.7.2. REACTION: CO + 3H2 CH4 + H2O

CO2 + 4H2 CH4 + 2H2

7
 INPUT OUTPUT

N2 = 250 kmol= 7020kg N2 = 250kmol= 7020kg

Ar = 2.25 kmol = 90kg Ar = 2.25kmol=90kg

CO = 10.33 kmol= 289.24kg CO = 4.65kmol= 130.2 kg

H2 = 800 kmol= 1600kg H2 = 800 kmol = 1600kg

CH4 = 17.85 kmol = 285.6kg CH4 = 30kmol = 480kg

H2O = 69.33 kmol= 1247.9kg H2O = 48.7kmol = 876.6kg

CO2 = 11.895 kmol= 523.38kg CO2 = 5.33kmol =234.52kg

TOTAL= 12921.72 Kg TOTAL= 10411.32 Kg

95% of CO2 is removed

=22.515kmol= 991kg

TOTAL = 12921.72 Kg

CH4 produced from methanation is 30 kmol, out of which 28 kmol are being recycled,
whereas, 2 kmol are being vented out.

Now, 1000 kmoles of (N2-H2) are fed to the reactor.

Let , X = moles of N2 and H2 recycled to the reactor

Y = moles of (N2-H2) purged out.

Moles of (N2-H2) entering the reactor = 1000+X

Moles of (N2-H2) leaving the reactor = 0.7 (1000+X)

(30% of feed is being converted to NH3)

Moles of NH3 formed = {0.3(1000+X)}/ 2

Moles of Ar in fresh feed = 2.25

8
Moles of Ar in total feed = 0.05(1000+x)

Moles of Ar per moles (N2-H2)leaving the reactor = {0.05(1000+X)}/{O.70(1000+x)}

= 0.714

Moles of Ar purged = 0.714y

At steady state, Ar purged = Ar in fresh feed

=> 0.714y = 2.25

=> y = 3.15

Making a (N2-H2) balance around bleed point ,

0.70 (1000+x) = x + y

=> x = 2228.3 kmol

Fresh (N2-H2) = 1000 kmol

Recycle (N2-H2) = 2228.3 kmol

Purge (N2-H2) =3.15 kmol

Ammonia formed = 484.245 kmol

Recycle ratio = (2228.3/1000) kmol = 2.228

Purge ratio = (3.15/ 2228.3) = 0.00141

1.8. AMMONIA SYNTHESIS LOOP:

CONDENSER

9
 FEED
REACTOR

REFRIGERATION
Liq. NH3
SECTION

RECYCLE

PURGELiq. NH3

1.8.1. MATERIAL BALANCE AROUND SYNTHESIS REACTOR:

1.8.2. ASSUMPTION: Assuming 30% conversion of (N2-H2) mixture.

R
N2 N2
E
H2 H2
A

Ar C Ar
T
N2 N2
O

H2 R H2

INPUT
N2 = 250 kmol(fresh feed) =7020 kg
N2 = 555kmol(recycle) =15584.4 kg
Ar = 2.25 kmol = 90 kg
H2 = 750 kmol(fresh feed) =1500 kg
H2O= 1665 kmol(recycle) =3330 kg
=27526.24 kg
OUTPUT
N2 = 563.5 kmol = 15823.08 kg
H2 = 1690.5 kmol =3381 kg
Ar = 2.25 kmol = 90 kg
NH3 = 484.245 kmol = 8232.165 kg
= 27526.245 kg

1.9. MATERIAL BALANCE OVER CONDENSER:

1.9.1. ASSUMPTION:30% of ammonia be condensed in the condenser.

10
Therefore, (8232.165*0.3) = 2469.65 kg

N2 N2

H2 H2

Ar Ar

NH3 Gas NH3

Liq. NH3

INPUT OUTPUT

N2 = 563.5 kmol = 15823.08 kg N2 = 563.5 kmol = 15823.08 kg

H2 = 1690.5 kmol =3381 kg
Ar = 2.25 kmol = 90 kg
NH3 = 484.245 kmol = 8232.165 kg
=27526.245 kg
H2 = 1690.5 kmol =3381 kg
Ar = 2.25 kmol = 90 kg
Gas NH3 = 338.97 kmol = 5762.49
kg
Liquid NH3 = 145.23 kmol = 2469.65
kg
= 27526.245 kg

1.10. OVERALL MATERIAL BALANCE:

11
Input = 3800 kg (natural gas) + 7000 kg (steam) + 9000 kg (air)

= 19800 kg

Output = CO2( from separator) +(CO, CO2, CH4, H2O vented out) + liq. NH +

Purge H2 + Ar

= 9910kg+(130+876.8 +234.63 +32)kg+(8291.4+220.5 +47.25)kg + 90 kg

= 19800.32 kg

CHAPTER – 2

MODIFIED MATERIAL BALANCE

12
2.1. CALCULATION OF THE MULTPLICATION FACTOR:

2.1.1. ASSUMPTIONS:

Working Days = 330days.

Desired production rate of ammonia = 1000tonnes/day

= (1000*103kg)/24hr

= 41667 Kg/hr

Therefore, multiplication factor for the modified material balance = 41667/8231.4

= 5.062

2.2. BASIS : 5062Kmol/hr N2-H2 mixture to the ammonia synthesis reactor.

2.3. MODIFIED MATERIAL BALANCE OVER PRIMARY

REFORMER:

2.3.1. REACTIONS:

CH4 + H2O CO + 3H2 (6.1)

C2H6 + 2 H2O 2CO + 5H2 (6.2)

2.3.2. ASSUMPTION: conversion of 86% of methane and 100% conversion of

ethane.

Natural Gas = 19235.6 Kg

Steam = 35434 Kg = 1968.5 Kmol.

2.3.3. COMPOSITION:

CH4 = 95% = 18273.82 Kg = 1142.1 Kmol

C2H6 = 5% = 961.8Kg = 32.06 Kmol.

2.3.4. INPUT:

13
CONSTITUENTS In Kg In Kmol
CH4 18270.4 1141.9
C2H6 956.7 31.89
H2O 35443.98 1969.11
TOTAL 54671.08 Kg 3142.9 Kmol

2.3.5. OUTPUT:

CONSTITUENTS In Kg In Kmol
CH4 2551.2 159.45
H2O 16610.4 922.8
CO 29282.65 1045.8
H2 6211.074 3105.537
TOTAL 54655.33 Kg 5233.587 Kmol

2.4. MODIFIED MATERIAL BALANCE OVER SECONDARY

REFORMER:

Air = 45558Kg

2.4.1. COMPOSITION:

N2 = 35534.8 Kg

Ar = 456 Kg

O2 = 9564.8 Kg

CH4 + 2O2 CO2 + 2H2O

2.4.2. ASSUMPTION:

Let, x be the amount of CH4 recycled to the reformer.

70% conversion of the reactants in the secondary reformer.

2.4.3. INPUT:

14
CONSTITUENTS In Kmol In Kg
N2 1265.5 35535.2
Ar 11.4 456
O2 301.2 9567.18
CH4 (159.4+x) (2551.25+16x)
H2O 922.8 16610.4
CO 1045.8 29282.65
H2 3105.5 6211.07

2.4.4. OUTPUT:

CONSTITUENTS In Kmol In Kg
N2 1265.5 35535.2
Ar 11.4 456
O2 301.2-1.4(159.4+x)
CO 1045.8 29282.65
H2 3105.5 6211.07
CH4 0.3(159.4+x)
H2O (922.8+1.4(159.4+x)
CO2 0.7(159.4 + x)

2.5. MODIFIED MATERIAL BALANCE OVER SHIFT

REACTOR:

CO + H2O CO2 + H2 ...............................................................(6.4).

2.5.1. ASSUMPTION: Assuming 95% conversion of the reactants in the shift

reactor.

INPUT OUTPUT

15
CONSTITUENTS AMOUNT(Kmol) CONSTITUENTS AMOUNT(Kmol
)
N2 1265.5 N2 1265.5
Ar 11.4 Ar 11.4
O2 301.2-1.4(159.4+x) O2 301.2-
1.4(159.4+x)
CO 1045.8 CO 52.29
H2 3105.5 H2 4049.6
CH4 .3(159.4+x) CH4 .3(159.4+x)
H2O 922.8+1.4(159.4+x) H2O 152.5+1.4x
CO2 .7(159.4+x) CO2 (1105.03+.7x)

2.6. MODIFIED MATERIAL BALANCE OVER CO2

SEPARATOR:

2.6.1. ASSUMPTION: 95% of carbon is being removed.

INPUT OUTPUT
CONSTITUENTS AMOUNT(Kmol) CONSTITUENTS AMOUNT(Kmol)
N2 1265.5 N2 1265.5
Ar 11.4 Ar 11.4
O2 301.2-1.4(159.4+x) O2 301.2-1.4(159.4+x)
CO 52.29 CO 52.29
H2 4049.6 H2 4049.6
CH4 .3(159.4+x) CH4 .3(159.4+x)
H2O 152.5+1.4x H2O 152.5+1.4x
CO2 (1105.03+.7x) CO2 .05(1105.03+.7x)

2.7. MODIFIED MATERIAL BALANCE OVER METHANATOR:

CO + 3H2 CH4 + H2O ...................................................(6.5)

16
CO2 + 4H2 CH4 + 2H2O ....................................................(6.6)

2.7.1. ASSUMPTION:55% conversion in the methanator.

INPUT OUTPUT
CONSTIT AMOUNT(Kmol) CONSTIT AMOUNT(Kmol)
UENTS UENTS
N2 1265.5 N2 1265.5
Ar 11.4 Ar 11.4
O2 301.2-1.4(159.4+x) O2 301.2-1.4(159.4+x)
CO 52.29 CO 23.53
H2 4049.6 H2 4049.6
CH4 .3(159.4+x) CH4 .3(159.4+x)+28.8+.0275(
1105.03+.7x)
H2O 152.5+1.4x H2O (152.5+1.4x)+28.8+.055(
1105.03+.7x)
CO2 .05(1105.03+.7x) CO2 .0225(1105.03+.7x)

Now,CH4 is recycled.Therefore,

.3(159.4+x)+28.8+.0275(1105.03+.7x) = x

 x = 157.91. Therefore, CH4 recycled =157.91kmol

Putting the values of x and then making the balance, we get –

2.8. MODIFIED MATERIAL BALANCE OVER SHIFT

REACTOR:

INPUT OUTPUT
CONSTIT Kmol Kg CONSTIT Kmol Kg

17
UENTS UENTS
N2 1265.5 35534 N2 1265.5 35534
Ar 11.4 456 Ar 11.4 456
O2 143.034 4554.68 O2 143.034 -4554.68
CO 1045.8 29282.4 CO 52.29 1464.12
H2 3105.5 6211 H2 4049.6 8099.2
CH4 95.193 1523.68 CH4 95.193 1523.68
H2O 1367.034 24606.612 H2O 373.574 6724.332
CO2 222.117 9773.15 CO2 1215.567 53484.95
TOTAL 102831.36 TOTAL 102730.8

2.9. MODIFIED MATERIAL BALANCE OVER CO2 REACTOR:

INPUT OUTPUT
CONSTIT Kmol Kg CONSTIT Kmol Kg
UENTS UENTS
N2 1265.5 35434 N2 1265.5 35534
Ar 11.4 456 Ar 11.4 456
O2 -142.334 -4554.68 O2 - -4554.68
142.334
CO 52.29 1464.12 CO 52.29 1464.12
H2 4049.6 8099.2 H2 4049.6 8099.2
CH4 95.043 1520.68 CH4 95.043 1520.68
H2O 373.574 6724.332 H2O 373.574 6724.332
CO2 1215.56 53484.64 CO2 60.778 2674.232
95% of 50810.4
CO2remove
d
TOTAL 102627.5 TOTAL 102727.5

18
6.10. MODIFIED MATERIAL BALANCE OVER METHANATOR:

INPUT OUTPUT
CONSTIT Kmol Kg CONSTIT Kmol Kg
UENTS UENTS
N2 1265.5 35534 N2 1265.5 35534
Ar 11.4 456 Ar 11.4 456
O2 -142.334 -4554.68 O2 -142.334 -4554.68
CO 52.29 1464.12 CO 23.53 658.84
H2 4049.6 8099.2 H2 4049.6 8099.2
CH4 95.193 1523.68 CH4 157.27 2516.32
H2O 373.574 6724.332 H2O 469.23 8446.14
CO2 60.778 2674.232 CO2 27.35 1203.4
TOTAL 56013.884 TOTAL 52358.42
CH4 produced from methanator is 151.86 kmol, out of which 141.7 kmol

are being recycled, whereas 10.1 kmol are being vented out

Now, 5062 kmol of (N2-H2) are fed to the reactor.

Let X= moles of N2 and H2 recycled to the reactor.

Y= moles of (N2-H2)purged out.

Moles of (N2-H2) entering the reactor = (5062 + X)

Moles of (N2-H2) leaving the reactor = .7(5062+X)

30% of feed is being converted to NH3

Moles of NH3 formed = {.3(5062+X)}/ { 2(5062+X)}

Moles of Ar in fresh feed = 11.38 kmol

Moles of Ar in total feed = .05(5062+X)

Moles of Ar per mole (N2-H2) leaving the reactor ={.05(5062+X)}/{.7(5062+X)}

= 0.714

19
Therefore, moles of Ar purged = 0.714Y

At steady state,

Moles of Ar purged = Moles of Ar in fresh feed

=> 0.714Y = 11.38

=>Y = 15.94 kmol

From (N2-H2) balance around bleed point,

.7(5062+X) = X+Y

=>X =11758.2 kmol

Therefore, NH3 formed = .3{(5062+X)/2} =2523.03 kmol

Fresh (N2-H2) = 5062 kmol

Recycle (N2-H2) = 11758.2 kmol

Purge (N2-H2) = 15.94 kmol

Therefore, Recycle ratio = 11758.2/5062 = 2.32

Purge ratio = 15.94/ 11758.2 = 0.0013

2.11. MODIFIED MATERIAL BALANCE AROUND

CONDENSER:

Let, 30% of ammonia being condensed in the condenser. Therefore, amount of

ammonia condensed =41667 * 0.3 = 12500.1

20
 INPUT OUTPUT
CONSTITU Kmol Kg CONST Kmol Kg
ENTS ITUEN
TS
N2 2819.53 79144 N2 2819.53 79144
H2 8579 17158 H2 8579 17158
Ar 11.4 456 Ar 11.4 456
NH3 2451 41667 Gas NH3 1715.5 29163.5
TOTAL 138424.2 TOTAL 125920.7

Liq. NH3 735 12495

TOTAL 138415.7

2.12. OVERALL MATERIAL BALANCE:

Input = 20036kg (natural gas) + 36434 kg (steam) + 48558 kg (air)

= 105028 kg

Output = CO2 (from separator) + ( CO2,CO,CH4, H2O vented out) +

Liq. NH3 + (purge N2+ Purge H2+ Ar)

= 50810.4 Kg + (1203.4 Kg +658.84 Kg + 161.6 Kg + 8446.14 Kg)

+ (41658 Kg) + (1122.8 Kg + 510.9 Kg + 456 Kg)

= 105028.08 Kg

21
CHAPTER -3

ENERGY BALANCE

3.1. ASSUMPTIONS:

(i) Datum temperature of 25°C(298K) is taken in all energy calculations.

(ii) There is no heat loss from any equipment by conduction, convection
and radiation.
(iii) Saturated steam is available at 42Kgf/cm2
(iv) Specific heat of water is 4.18 kJ/kg.K
(v) No heat loss from any equipment due to conduction, convection
and radiation.

The mean heat capacities are calculated as –

Cpm= a + b/2(T1+T2) + c/3(T12 +T22 +T1T2) + d/4(T12+T22) (T1+T2)

Cpmvalues are taken from Donald Q Kern.

Assuming the datum temperature of 25°C(298K),

Enthalpy, H = mCpm(T1-T2)

H = m[Cp1Ts+λs + Cpg(T-Ts)...... (For phase change )

Where, m = mass flow rate (taken from modified material balance)

Cpm = mean specific heat

Cpg = specific heat of gases

λ = latent heat of vaporisation

T1 = temperature of the component

T2 = reference temperature

22
3.2. ENERGY BALANCE OVER NATURAL GAS COMPRESSOR:

T1 T2 T1 T2

P1 P2 P2 P3

T1=30ºC = 303K , P1= 1Kg/cm2 P3= 42Kg/cm2

Assuming perfect intercooling,

P2/P1 = P3/P2

P22 = P1x P3

P22 = 1x42

P2= 6.48 Kg/cm2

Temperature of the steam after compression,

T2 = T1(P2/P1)ˠ-1/ˠ

= 303x(6.48/1)1.4-1/1.4

= 516.8K = 243.8ºC (since ɤ = 1.4 )

3.2.1. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUE Cp(INPUT) at 303K (KJ/KgK) Cp(OUTPUT)at

NTS 516.8K(KJ/KgK)

CH4 2.3054 2.9477

C2H6 1.7794 2.6585

23
3.2.2.ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)

CH4 18270.4*2.3054(303-298) 210602.9

C2H6 956.7*1.7794(303-298) 8511.76

TOTAL 219114.66

3.2.3. ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY(KJ)

CH4 18270.4*2.9477(516.8- 11783617.99

298)

C2H6 956.7*2.6585(516.8-298) 556493.065

TOTAL 12340111.06

Therefore, power required by the compressor= {Total output-total input/3600}KW

={12340111.06-219114.66/3600}KW

= 3366.94 KW

3.2.4. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUENTS Cp (INPUT) at 516.8K Cp(OUTPUT)

(KJ/KgK) at303K(KJ/KgK)

CH4 2.9477 2.3054

24
 C2H6 2.6585 1.7794

Cooling water 4.179(at 30˚C) 4.208(at 90ºC)

3.2.5. ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)

CH4 18270.4*2.9477(516.8-298) 11783617.99

C2H6 956.7*2.6585(516.8-298) 554458.355

Cooling water m*4.179(303-298) 20.895m

TOTAL (12338076.35+20.895m)

3.2.6. ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY(KJ)

CH4 18270.4*2.3054(303-298) 210602.9

C2H6 956.7*1.7794(303-298) 8511.76

Cooling water m*4.208(363-298) 273.52m

TOTAL (219114.66+273.52m)

Therefore, amount of cooling water needed for perfect inter-cooling,

m = (12338076.35-219114.66) / (273. 52-20.895)

= 47972.14 Kg

25
3.2.7. MODIFIED ENTHALPY OF INPUT AND OUTPUT
STREAM:

CONSTITUENTS ENTHALPY (INPUT) KJ ENTHALPY

(OUTPUT) KJ

CH4 11783617.99 210602.9

C2H6 554458.355 8511.76

Cooling water 1002377.865 13121339.73

TOTAL 13340454.21 13340454.39

3.3. ENERGY BALANCE OVER FURNACE-1:

Outlet furnace temperature = 800ºC (1073K)

3.3.1. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUENTS Cp (INPUT) at Cp(OUTPUT)at

516.8K(KJ/KgK) 1073K(KJ/KgK)
CH4 2.9477 4.647
C2H6 2.6585 4.2922

3.3.2. ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)

CH4 18270.4*2.9477(516.8-298) 11783617.99

26
 C2H6 956.7*2.6585(516.8-298) 556493.065
TOTAL 12340111.06

3.3.3. ENTHALPY OF OUTPUT STREAMS:

COMPONENTS ENTHALPY(KJ)

CH4 18270.4*4.647(1073-298) 65799475.32

C2H6 956.7*4.2922(1073-298) 3182419.499
TOTAL 68981894.82

Therefore, heat added to the feed,

Q= ΔH output –ΔH input

= (68981894.82-12340111.06) KJ

= 56641783.76 KJ

Let, the efficiency of the furnace be 80%

Actual heat generated in the furnace,

Qʹ = Q/0.8

= 56641783.76/0.8 KJ

= 70802229.7 KJ

Again, Calorific value of the fuel gas,

C= 11000 Kcal/Kg = 45980 KJ/Kg

Therefore, amount of fuel gas required,

m = Qʹ/C

= 70802229.7/45980

=1539.85 Kg

27
3.4. ENERGY BALANCE OVER PRIMARY REFORMER:

3.4.1 REACTION:

CH4 + H2O CO + 3H2 ; ΔHº298 = 206.284 KJ/mol

C2H6 + 2H2O 2CO + 5H2; ΔHº298 = 347.3 KJ/mol

Cp values of the various components,

H2O (v) = 30.475 +9.652x10-3T + 1.189x10-6T2

N2 = 27.034 + 5.815x10-3T – 0.2889x10-6T2

O2 = 25.611 + 13.260x10-3T – 4.2077x10-6T2

CO2 = 26.75 + 42.26x10-3T – 14.25x10-6T2

H2 = 26.88 + 4.35x10-3T – 0.33x10-6T2

CH4 = 13.41 + 77.03x10-3T – 18.74x10-6T2

CO = 27.588 + 5x10-3T

Input temperature to the primary reformer = 800ºC (1073K)

3.4.2. ENTHALPY OF INPUT STREAM:

INPUT Cp at 1073 (KJ/KmolK) mCpΔT (KJ)

CH4 74.48 65912751.8
C2H6 75 1853606.25
H2O 40.8 62354821.82
ΣmCpΔT= 130121179.9

REACTION 1: CH4 + H2O CO + 3H2

Heat of reaction at 298K = 206.284 KJ/mol

Therefore, heat of reaction at 1073K = 226361.815 KJ/kmol

28
REACTION 2: C2H6 + 2H2O 2CO + 5H2

Heat of reaction at 298K = 347.3 KJ/mol

Therefore, heat of reaction at 1073K = 408110.650 KJ/kmol

For Energy Balance,

Input enthalpy + Heat of reaction = Output enthalpy

 130121179.9 + (226361.815+408110.650) = (T-298)*

[15.97(13.41+77.03*10-3T-18.79*10-6T2) + 92.46(30.475+9.652*
10-3T+1.189*10-6T2) + 104.74(27.588+5*10-3T) +311.045(26.88+
4.35*10-3T – 0.33*10-6T2)]
Solving the equation by trial and error, we have,
T = 988 K (715ºC)
Therefore, output temperature from the primary reformer = 715ºC (988K)

3.5. ENERGY BALANCE OVER AIR COMPRESSOR:

T1 T2 T1T2

P1 P2 P2 P3

P1= 1Kg/cm2

P3= 42 Kg/cm2

T1= 30ºC = 303K

Assuming perfect inter-cooling,

P2/P1= P3/P2

=> P22 /P1P3

=> P22 =1x42

=> P2 = 6.48 Kg/cm2

Temperature of the stream after compression,

29
T2 = T1(P2/P1)ɤ-1/ɤ= 303*(6.48/1)1.4-1/1.4

= 516.8K = 243.8ºC (since ɤ = 1.4)

3.5.1.SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

Cp(input)at Cp(output)at
CONSTITUENTS 303K(KJ/Kg K) 516.8K(KJ/KgK)

N2 1.0156 1.0475
O2 0.8234 1.0059
Ar 0.52 0.52

3.5.2. ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 35534*1.0156x303-298) 180441.65
O2 9567.18*0.8234(303-298) 39308.08
Ar 456*0.52(303-298) 1185.6
TOTAL 220935.33

3.5.3. ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 35534*1.0475(516.8-298) 8144144.06
O2 9567.18*1.0059(516.8-298) 2105649.45
Ar 456*0.52(516.8-298) 51881.86
TOTAL 10301675.37

Therefore, power required by the compressor= (total output-total input/3600) KW

= (10301675.37-220935.33/3600) KW

= 2800.2 KW

30
3.6. INTERCOOLER OF AIR COMPRESSOR:

3.6.1. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

Cp(INPUT)at Cp(OUTPUT)at
CONSTITUENTS 516.8K(KJ/KgK) 303K(KJ/KgK)

N2 1.0475 1.0156
O2 1.0059 0.8234
Ar 0.52 0.52
Cooling Water 4.179(at 30ºC) 4.208(at 90ºC)

3.6.2. ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 35534*1.0475(516.8-298) 8144144.06
O2 9567.18*1.0059(516.8-298) 2105649.45
Ar 456*0.52(516.8-298) 51881.86
Cooling Water m*4.179(303-298) 20.895m
TOTAL (10301675.37+20.8
95m)

3.6.3.ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY(KJ)

N2 35534*1.0156(303-298) 180441.65
O2 9567.18*0.8234(303-298) 39388.08

31
 Ar 456*0.52(303-298) 1185.6
Cooling Water m*4.208(363-298) 273.52m
TOTAL (221015.33+273.52m)

Therefore, amount of cooling water needed for perfect inter-cooling,

m = (10301675.37–221015.33 )/(273.52 – 20.895= 39903.65 Kg

3.6.4. MODIFIED ENTHALPY OF INPUT AND OUTPUT

STREAM:

CONSTITUENTS ENTHALPY(INPUT)KJ ENTHALPY(OUTPUT)

KJ
N2 8144144.06 180441.65
O2 2105649.45 39388.08
Ar 51881.86 1185.6
Cooling Water 833786.77 10914446.35
TOTAL 11135462.14 11135461.68

3.7. ENERGY BALANCE OVER FURNACE-2:

Outlet furnace temperature = 715ºC (988K)

3.7.1. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

32
CONSTITUENTS Cp(INPUT)at Cp(OUTPUT)at
516.8K(KJ/KgK) 988K(KJ/KgK)
N2 1.0475 1.1178
O2 1.0059 1.0884
Ar 0.52 0.52

3.7.2. ENTHALPY OF INPUT STREAM:

CONSTITUENTS ENTHALPY(KJ)
N2 35534*1.0475(516.8-298) 8144144.062
O2 9567.18*1.0059(516.8-298) 2105649.45
Ar 456*0.52(516.8-298) 51881.86
TOTAL 10301675.37

3.7.3. ENTHALPY OF OUTPUT STREAM:

CONSTITUENTS ENTHALPY(KJ)
N2 35534*1.1178(988-298) 27406734.59
O2 9567.18*1.0884(988-298) 7184913.91
Ar 456*0.52(988-298) 163612.8
TOTAL 34755261.3

Therefore, heat added to the feed,

Q = ΔHoutput - ΔHinput

= (34755261.3–10301675.37) KJ

= 24453585.93 KJ

Let the efficiency of the furnace be 80%

Actual heat generated in the furnace,

Qʹ = Q/0.8

33
 = 24453585.93/0.8

= 30566982.41KJ

Again, calorific value of the fuel gas, C = 11000 Kcal / Kg= 45980 KJ / Kg

Therefore, amount of fuel gas required,

m = Qʹ/C= 30566982.41/45980

= 664.78 Kg

must be circulate in the reformer in order to keep the reactor temperature constant.

Therefore, amount of cooling water that must be circulated is,

888304.57 = m Cp ∆T

m = 888304.57/{75.24x(323-298)} = 196.7Kg/hr

34
3.8. ENTHALPY BALANCE OVER HEAT EXCHANGER – 1:

3.8.1. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUENTS Cp(INPUT)at Cp(OUTPUT)at

1048K(KJ/KgK) 523K(KJ/KgK)
N2 1.1268 1.084
Ar 0.52 0.52
CO 1.173 1.07898
H2 15.6099 14.7212
CH4 4.5436 2.9663
H2O(g) 2.2871 2.0122
CO2 1.2832 1.0505
At 34 Kgf/cm2, saturated temperature of water, Ts = 240.9ºC = 513.9 K

λwater = 1760.3 KJ/Kg

Cp of water at 513.9K = 4.78 KJ/ KgK

3.8.2. ENTHALPY OF INPUT OF HOT STREAM:

CONSTITUENTS ENTHALPY(KJ)
N2 35534*1.1268(1048-298) 30029783.4
Ar 456*0.52(1048-298) 177840
CO 29282.4*1.173(1048-298) 25761191.4
H2 6211.07*15.6099(1048-298) 72715636.19
CH4 1523.09*4.543(1048-298) 5190226.978
H2O 24606.612{4.78*513.9+1760. 133817697.8
3+2.2871(1048-513.9)}
CO2 9773.15*1.2382(1048-298) 8625672.6
TOTAL 276768209.7

35
3.8.3. ENTHALPY OF OUTPUT OF HOT STREAM:

CONSTITUENTS ENTHALPY(KJ)
N2 35534*1.0484(523-298) 8382115.26
Ar 456*0.52(523-298) 53352
CO 29282.4*1.07898(523-298) 7108902.88
H2 6211.07?*14.7212(523-298) 20572740.83
CH4 1523.09*2.9663(523-298) 1016535.585
H2O 24606.612{4.78*513.9+1760.3+ 104210306.5
2.0122(523-513.9)}
CO2 9773.148*1.0505(523-298) 2310005.694
TOTAL 136110058.8
Cooling water entering at 30ºC and leaving at saturated temperature i.e., at 240.9ºC.

Recycled CH4 is entering at 367ºC and leaving at 715ºC.

Cp of CH4 at 367ºC = 3.3179 KJ/KgK

Cp of CH4 at 715ºC = 4.3634 KJ/KgK

Amount of CH4 entering = 2515.04 Kg

Enthalpy of CH4 input,ΔH = 2515.04*3.3179*(640-298) = 2853870.716KJ

Enthalpy of CH4 output,ΔH = 2515.04*4.3634*(988-298) = 7572146.62KJ

Cp of H2O at 30ºC = 4.179KJ/KgK

Cp of H2O at 240.9ºC = 4.78 KJ/KgK

Now, enthalpy of cooling water entering = m*4.179*(303-298) = (20.895m) KJ

Enthalpy of water leaving the exchanger = m*{4.78*(513.9)+1760.3}

= (4216.742m) KJ

Therfore, amount of cooling water required,

m ={(276768209.7+2853870.716)-(136110058.8+7572146.62)}/ (4216.742-20.895)

= 32398.69 Kg

36
3.8.4. MODIFIED ENTHALPY OF INPUT AND OUTPUT
STREAM:

CONSTITUENTS ENTHALPY(INPUT)KJ ENTHALPY(OUTPUT)KJ

N2 30029783.4 8382115.26
Ar 177840 53352
CO 25761191.4 7108902.889
H2 72715636.19 20572740.83
CH4 5190226.978 1016535.585
H2O(g) 133817697.8 104210306.5
CO2 9075833.89 2310005.694
CH4(recycle) 2853870.716 7572146.62
Cooling Water 676970.63 136616916.9
TOTAL 280299051 287843022.3

3.9. ENERGY BALANCE OVER SHIFT REACTOR:

Input temperature to the shift converter = 250ºC(523K)

3.9.1. REACTION:

CO + H2O CO2 + H2 ; ∆Hº = - 41.190 KJ/mol

3.9.2. ENTHALPY OF INPUT STREAM:

INPUT CP at 523K(KJ/Kmol K) mCp∆T(KJ)

N2 29.99 8539277.625
Ar 20.774 53285.31
CO 30.395 7152095.475
H2 29.06 20305311.75
CH4 48.57 1040292.902
H2O 35.84 11023762.18
CO2 44.95 2246435.809
TOTAL 52758206.55

37
Heat of reaction at 298K = -41.190 KJ/mol

Therefore, Heat of reaction at 523K = 39849.86KJ/Kmol

For energy balance,

Input enthalpy + Heat of generation = Output enthalpy.

52758206.55+39849.85=(T-298)*[1.14*20.77+5.237(27.588+5*103T)+

126.75(27.034+5.815*10-3T-0.28*10-6T2)+15.21(30.475 + 9.652*10-3T

-1.189*10-6T2)+ 9.019(13.41+77.03*10-3T – 18*10-6T2) + 405.6(26.88+4.35*10-3T

-0.33*10-6T2)+120(26.75+ 42.26*10-3T-14.25*10-6T2)]

Solving the equation by tail and error, we have, T=528K(255ºC)

Therefore, Output temperature from the primary reformer = 255ºC(528K)

Since, exothermic reaction takes place in the shift reactor, cooling water must

be circulated in the reactor in order to keep the reactor temperature constant.

Therefore, amount of cooling water that must be circulated is,

39849.86 = mCp∆T

=>m =39849.86/[75.24*(363-303)]

=8.82 kg/hr.

38
3.10. ENERGY BALANCE OVER HEAT EXCHANGER-2:

3.10.1. SPECIFICHEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUENTS CP(Input) at Cp(Output)at

528K(KJ/kg.K) 373K(KJ/kgK)
N2 1.0492 1.026
Ar .52 .52
CO 1.0799 1.0521
H2 14.7296 14.4672
CH4 2.9814 2.5157
H2O 2.014 4.219
CO2 1.0531 0.9459
At 30 Kgf/cm2, saturated temperature of water, Ts = 233.8ºC = 506.8K

λwater = 1794.02KJ/kg.

Cp of H2O at 506.8K = 4.7263KJ/KgK

3.10.2. ENTHALPY OF INPUT HOT STREAM:

COMPONENT ENTHALPY(KJ)
N2 35534*1.0492(528-298) 8574922.744
Ar 456*0.52(528-298) 54537.6
CO 1464.12*1.0799(528- 363623.7332
298)
H2 8099.2*14.7296(528- 26599149.66
298)
CH4 1523.68*2.9814(528- 1044820.897
298)
H2O 2372.4[4.7263*506.8+17 10039962.73
94.02+(528-298)*2.014
CO2 53484.95*1.0531(528- 12954750.19
298)
TOTAL 59631767.55

39
7.11.3. ENTHALPY OF OUTPUT OF HOT STREAM:

COMPONENT ENTHALPY(KJ)
N2 35534*1.026(373-298) 2734341.3
Ar 456*0.52(373-298) 17784
CO 1464.14*1.0521(373-298) 115531.6271
H2 8099.2*14.4672(373-298) 8787955.968
CH4 1523.68*2.5157(373-298) 287484.1332
H2O 2372.43*4.219*(373-298) 750686.67
CO2 53484.95*0.9459(373- 3794356.065
298)
TOTAL 16488139.76

Cooling water entering at 30ºC and leaving at 90ºC.

Cp of H2O at 30ºC = 4.179KJ/KgK.

CP of H2O at 90ºC = 4.208KJ/KgK

Now, Enthalpy of cooling water entering = m*4.179*(300-298)= (20.895m)

Enthalpy of water leaving the exchanger = m *4.208*(363-298) = 273.52KJ

Therefore, amount of cooling water required,

m = {(6065181.152-1655141.5)/(273.52-20.895)}Kg = 170781.3kg.

40
3.10.4. MODIFIED ENTHALPY OF INPUT AND OUTPUT
STREAM:

CONSTITUE ENTHALPY(INPUT) ENTHALPY(OUTPUT)

NTS KJ KJ
N2 8574922.744 2734341.3
Ar 54537.6 17784
CO 363623.7332 115531.6271
H2 26599149.66 8787955.968
CH4 1044820.897 287484.1332
H2O 1003996.273 75068.667
CO2 12954750.19 3794356.065
Cooling water 3568475.264 46712101.18
TOTAL 63200242.81 63200240.94

41
3.11. ENERGY BALANCE OVER HEAT EXCHANGER-3:

3.11.1. SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUENTS CP(INPUT)at373K(KJ/KgK) CP(OUTPUT)at

600K(KJ/KgK)
N2 1.026 1.0599
Ar .52 .52
CO 1.0521 1.0928
H2 14.4672 14.8515
CH4 2.5157 3.1977
H2O(l) 4.219 2.0418
CO2 0.9459 1.0869

At 23kgf/cm2, saturated temperature of water,Ts = 219.6ºC =492.6K

λwater = 1858.2KJ/Kg

Cp Of H2O at 492.6K = 4.63KJ/kg.K

3.11.2. ENTHALPY OF INPUT OF COLD STREAM:

CONSTITUENTS ENTHALPY(KJ)
N2 35534*1.026(373-298) 2734341.3
Ar 456*0.52(373-298) 17784
CO 1464.14*1.0521(373-298) 115531.6271
H2 8099.2*14.4672(373-298) 8787955.968
CH4 1523.68*2.5157(373-298) 287484.1332
H2O 2372.43*4.219*(373-298) 750696.1628
CO2 2674.232*0.9459(373-298) 189716.7037
TOTAL 12883509.89

42
3.11.3. ENTHALPY OF OUTPUT OF COLD STREAM:

CONSTITUENTS ENTHALPY
N2 35534*1.0599(600-298) 11374070.95
Ar 456*0.52(600-298) 71610.24
CO 1464.14*1.0928(600-298) 483203.682
H2 8099.2*14.8515(600-298) 36326151.18
CH4 1523.68*3.1977*(600-298) 1471426.004
H2O 2372.43*(4.63*492.6+ 11282810.8
1858.2+2.0428*(600-298)
CO2 2674.232*1.0869*(600-298) 877800.0738
TOTAL 61887072.93

Steam is entering the exchanger at 500ºC and leaving the 350ºC.

Cp of H2O(g) at 500ºC = 2.1217KJ/kgK

Cp of H2O(g) at 350ºC = 2.0513KJ/kgK

Enthalpy of steam entering at 773K,

∆H = m[4.63*492.6+ 2.1217*(773-492.60)]

= 4733.862m

Enthalpy of steam leaving the exchanger at 623K,

∆H = m[4.63*492.6+2.0513(623-492.6)]

=4406.427m

Therefore, amount of stream supplied,

m = (61887072.93-12883509.89)/(4733.862-4406.427)kg

= 149658.9034

43
3.11.3. MODIFIED ENTHALPY OF INPUT AND OUTPUT
STREAM:

CONSTITUENTS ENTHALPY(INPUT) ENTHALPY(OUTPUT)

N2 2734341.3 11374070.95
Ar 17784 71610.24
CO 115531.6271 483203.682
H2 8787955.968 36326151.18
CH4 287484.1332 1471426.004
H2O 750696.1628 11282810.8
CO2 189716.7037 877800.0738
Steam 708464595.8 659461032.7
TOTAL 721348102.7 721348105.6

3.12.ENERGY BALANCE OVER METHANATOR:

3.12.1. REACTION:

CO + 3H2 CH4 + H2O; ∆Hº298 = -206.175KJ/mol

CO2 + 4H2 CH4 + 2H2O; ∆Hº298 = -164.987KJ/mol

Input temperature to the methanator is 327ºC(600K)

3.12.2. ENTHALPY OF INPUT STREAM:

INPUT Cp at 600(KJ/kmolK) mCp∆T

N2 30.41 11622124.21
Ar 20.74 71403.672
CO 30.588 485804.1218
H2 29.37 35918899.1
CH4 52.88 1520209.364
H2O(l) 36.69 4141181.211
CO2 46.97 862132.2833
TOTAL 54621753.97

44
REACTION 1: CO + 3H2 CH4 + H2O

Heat of reaction at 298 K = -206.175KJ/mol

Therefore, Heat of reaction at 600K = -217346.606KJ/kmol

REACTION 2: CO2 + 4H2 CH4 + 2H2O

Heat of reaction at 298K = -164.987KJ/mol

Therefore, Heat of reaction at 600K = -178184.02KJ/kmol

For energy balance,

Input enthalpy + Heat of generation = Output enthalpy

=>54621753.97+217346.606+178184.02=(T-298)*[126.75(27.034+5.815*

10-3T-0.2881*10-6T2)+1.14*20.74+2.353(27.588+5*10-3T)+382.78(26.88+4.35*

10-3T-.33*10-6T2)+15.21(13.41+77.03*10-3T2-18.74*106T2)+24.69(30.475+9.652*

10-3T+1.189*10-6T2)+2.702(26.75+42.26*10-3T-14.25*10-6T2)]

Solving the equation by trial and error, we have,

T=640K(367ºC)

Therefore, Output temperature of from the Methanator = 640K(367ºC)

Since, exothermic reaction takes place in the methanator, cooling water must be
circulated in the methanator in order to keep the reactor temperature constant.

Therefore, amount of cooling water that must be circulated is,

217346.606 = mCp∆T

=>m = 217346.606/[75.24*(363-303)]

= 48.14kg/hr

45
3.13. ENERGY BALANCE OVER SYNTHESIS GAS
COMPRESSOR:

3.13.1. ENERGY BALANCE OVER COMPRESSOR:

T1 T2 T1 T2

P1 P2 P2 P3

P1 = 20kg/cm2

P2 = 200kg/cm2

T1 = 230.8ºC =503.8K

Assuming perfect inter-cooling,

P2/P1 = P3/P2

=>P22 = P1.P3

= 20*200

=>P2 = 63.2455 kg/cm2

Temperature of the steam after compression,

T2 = T1.(P2/P1)γ-1/γ

=503.8*(63.2455/20)1.4-1/1.4

= 700K = 427ºC [Since γ = 1.4]

3.13.2.SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

CONSTITUENTS Cp(INPUT)AT503.8K Cp(OUTPUT)AT700K

(KJ/kgK) (KJkgK)
N2 1.0455 1.0748
Ar 0.52 0.52
H2 14.6887 15.0208

46
3.13.3. ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY
N2 35534*1.0455*(503.8-298) 7645634.023
Ar 456*0.52*(503.8-298) 48799.296
H2 7763*14.6887*(503.8-298) 23467040.21
TOTAL 31161473.53

3.13.4. ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY
N2 35534*1.0748*(700-298) 15353161.17
Ar 456*0.52*(700-298) 95322.24
H2 7763*15.0208*(700-298) 46875801.1
TOTAL 62324284.51

Therefore, Power required by the compressor={(Total output – Total

Input)/3600}KW

= {(62324284.51-31161473.53)/3600}

= 8656.3 KW

47
3.14. ENERGY BALANCE OVER AMMONIA SYNTHESIS
REACTOR:

Input temperature = 700K (427˚C)

Reaction: N2+ H2 2NH3 , ∆ Hº298 = -94.21KJ/mol

3.14.1 ENTHALPY OF INPUT STREAM:

INPUT Cp(KJ/Kmol) mCpΔT(KJ)

N2 30.97 5100366.92
Ar 20.774 9520.308
H2 29.49 14853697.19
TOTAL 19963584.42
Heat of reaction at 298K = -94.2KJ/mol

Therefore, heat reaction at 700K = -107488.219

For energy balance,

Input enthalpy + heat of generation = output enthalpy

 19963584.42+107488.219=(T-298)*[286.40(27.034+5.815*10-3T-0.28)*
10-6T2)+(20.774)(1.14)+859.26(26.88+4.35*10-3T-
0.33*106T2)+295.48(25.48+36.89*10-3T-6.305*10-6T2)
Solving by trial and error method, T= 723.5K(450.5˚C)

Output temperature from ammonia synthesis reactor = 723.5K(450ºC)

Since, exothermic reaction takes place in the synthesis reactor, cooling water must be
circulated in the reactor in order to keep the reactor temperature constant.

Therefore, amount of cooling water that must be circulated is,

107488.219 => m =107488.219/[75.24x(363-303)]=23.81Kg/hr

48
3.15. ENERGY BALANCE OVER CONDENSER:

COMPONENTS Cp at K(KJ/KgK)
N2 1.0186
Ar 0.52
H2 14.3826
NH3 2.1477

Saturation temperature of NH3 at 20kg/cm2 = 50˚C

Latent heat f condensation of NH3 at 50˚C= - 1052.58KJ/Kg

3.15.1 ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 80068*1.0186(298-2?8) 2038937.62
Ar 456*0.52(323-298) 5928
H2 17158*15.0606(323-298) 6460244.37
NH3 41667*2.1477(323-298) 2237205.398
TOTAL 10742309.39

3.15.2 ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 86008*1.0189(323-298) 2038931.62
Ar 456*0.52(323-298) 5928
H2 17158*14.3826(323-298) 6169416.27
NH3 29163.5*2.1477(323-298) 1565861.224
TOTAL 9780137.114

Amount of heat evolved during condensation of NH3 =12495*1052.58

=13151987.1

49
Therefore, amount of heat removed by cooling water = (Heat output- heat input) +
Heat evolved during condensation.

={9780137.114-10742309.39) + 13151987.1

= 12189814.82KJ

Cooling water entering at 30˚C and leaving at 90˚C

Shift Heat of H2O AT 30˚C = 4.179KJ/KgK

Specific Heat of H2O AT 90˚C = 4.203KJ/KgK

Enthalpy of input cooling water,

∆H˚363K = m*4.208(363-298) = (273.52m)KJ

Therefore, amount of cooling water supplied,

m = 12189814.82/(273.52-20.895) = 48252.606 kg

3.16.ENERGY BALANCE OVER REFRIGERATION SECTION:

3.16.1 SPECIFIC HEAT OF INPUT AND OUTPUT STREAMS:

COMPONENTS Cp (INPUT) at Cp(OUTPUT)at

323K(KJ/KgK) 238K(KJ/KgK)
N2 1.0186 1.0059
Ar 14.3826 14.2387
H2 0.52 0.52
NH3(g) 2.1477 5.2488

At 1kg/cm2, boiling point of NH3= -33.4˚C = 239.6K

50
Latent heat of condensation of NH3 AT -33˚C = 1375.6KJ/KgK

3.16.2 ENTHALPY OF INPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 79144*1.0186(323-298) 2015401.96
H2 17158*14.3826(323-298) 6169416.27
Ar 456*0.52(323-298) 5917.6
NH3 29163.5*2.1477(323-298) 1565861.224
TOTAL 9756597.054

3.16.3 ENTHALPY OF OUTPUT STREAM:

COMPONENTS ENTHALPY(KJ)
N2 79144*1.086(298-238) 5157023.04
H2 17158*14.382(298-238) 14805981.36
Ar 456*0.52(298-238) 14202.24
NH3(l) 29163.5{2.1477*239.6+1375.6 55369348.65
+5.2468(239.6-238)
TOTAL 75346555.29

Therfore, amount of heat to be removed = (9756597.054 + 75346555.29)

Ammonia is used as refrigerant as of its good refrigerant properties. It enters the

chamber at 40˚C and leaves at 15 ˚C

Specific heat of NH3 At -40˚C = 5.099KJ/KgK

Specific heat of NH3 at 15˚C = 4.6975KJ/KgK

Enthalpy of input NH3 = m*5.0995 * (298-238)

= (331.467m) KJ

Enthalpy of output NH3 = m*4.6975(298-238)KJ = (46.975m)KJ

Therefore, the amount of heat absorbed by NH3 = (331.4675+46.975)m KJ

51
46.975 =299140.23Kg

3.17.OVERALL ENERGY BALANCE :

Input = Natural Gas + air + furnace + cooling water + steam + refrigerant

=
67766358.05+43833663.1+70802229.7+62354821.82+1002377.865+833786.77+305
66982.41 +
676970.63+3568475.264+708464595.8+1776873.463+2661375.464+5615648.995+1
064880+2073460+1681840+398498.6+673040 = 1005815878 KJ

Output =NH3 + CO2 + vent + purged gas + cooling water + steam + refrigerant

=
13121339.73+10914446.35+136616916.9+46712101.18+659461032.7+23259652.05
+34837971.62+73510041.31+16661150+4394871+5928+511180+4802050

= 1024808681 KJ

Energy Loss = (Output- Input)

= (1024808681-1005815878) KJ

= 18992802 KJ

Therefore, percentage energy loss = (output-input)/input

=[(1024808681-1005815878)/1005815878]*100%

= 1.88%

52
CHAPTER- 4

DESIGN

4.1. DESIGN OF A STORAGE TANK:

In case of a storage tank since the pressure exerted by the liquid molecules is highest
at the bottom of the hydrostatic head and gradually decreases towards the top, hence
the thickness of the plate is also highest towards the bottom and decreases towards the
top. Therefore, in the design and fabrication of a storage tank several number of plates
of varying thicknesses are used.

It is required to determine the optimum diameter (D) to height (H) ratio for a large
storage tank such that cost is minimum.

Properties required in the design of the tank are:

 Material to be stored : Liquid NH3

 Specific gravity of liquid NH3 : 0.91
 Material of construction : Steel
 Material specification : IS:2002-1962
 Grade of material used : 2B
 Allowable Stress value: 12.1 kgf/mm2
=1200 kgf/cm2

4.1.2. ASSUMPTIONS:

1) The shell thickness is dependent upon ‘D’ and ‘H’.

2) The joints are double welded butt joints of joint efficiency of 0.85.
3) A corrosion allowance of 0.5mm is taken.
In case of storage tank design the tank is designed based on cost analysis

Let,

C1 = annual cost of fabricated shell in Rs/ft2 of shell area.

C2 = annual cost of fabricated bottom in Rs/ft2 of bottom area.

C3 = annual cost of fabricated roof in Rs/ft2 of roof area.

53
 C4 = annual cost of installed foundation under the vessel, Rs/ft2 of tank bottom
area.

C5 = annual cost of land in the tank area, chargeable to the tank, Rs/ft2 of tank
bottom area.

C = total annual cost of the vessel, Rs/yr.

D = diameter of the vessel, in ft.

H = height of the vessel in ft.

V = volume of the vessel in ft3 =πDH

A1= area of the shell in ft2 =πDH

A2 = area of the vessel bottom or projected area of the roof in ft2 = π/4D2

Assuming the ratio of annual cost of the shell per unit area C1 is two times the annual
cost of the bottom per unit area C2 and annual cost of the roof C3 1.8times the bottom
annual cost per unit area. The annual cost of landing the tank per unit area and annual
cost of installed foundation per unit tank bottom area together is estimated as 0.4
times the cost of the bottom tank per unit area. This is expressed as:

C1 = 2C2 (8.1.1)

C3 = 1.8C2 (8.1.2)

C4 + C5 = 0.4C2 (8.1.3)

For minimum cost, the optimum (D/H) is:

D/H =4C1/(C2 + C3+C4 +C5)

= (4*2C2)/(C2 +1.8C2 + 0.4C2)

= 2.5

Assuming that the NH3 is stored for 1month.

Mass flow rate of NH3 = 41667 kg/hr

= 41667*24*30 = 30000240 kg

54
Referring Perry’s Chemical Engineering Handbook,pg 831:

Density of NH3 (at 25ºC) = 0.993 g/cc

= .993*103 kg/m3

Volume of NH3,V = m/ρ = 30000240/.993*103

= 30211.7 m3/month.

For design purpose,

V = 31000 m3/month

Or.π/4 D2H = 31000

π/4(2.5H)2H = 31000

H3= 6318.47.

H = 18.5

Or H=18.5m = 60.68ft

D = 21.45m = 15.17ft.

Now, D(H-1) >1720(for a large tank) (11.1.4)

D(H-1) =15.17(60.68-1) = 9055.11>1720

So, the assumption of a large tank is acceptable.

So,D= 46.25 m ~ 50m

H=18.58m ~ 20m.

4.1.3. DESIGNING OF SHELL COURSES:

Thickness of the shell plane will be, t = 50(H-0.3) DG/SE (8.1.5)

Where,

S = kgf/cm2

t = minimum calculated thickness in ‘mm’

55
 D = nominal diameter of tank in ‘m’

H = height of tank in ‘m’

G = specific gravity of liquid to be stored.

E = weld joint efficiency factor.

Circumference of the tank = π D

=π*(46.25)

=145.225m.

Let, the total no of plates be ‘n’

Effective circumference = π D -(2n*10-3)

Length of each plate = {π D-(2n*10-3)}/n

Let us consider 18 shell plates.

So,Length of each plate = [π(50)-18*2*10-3]/18

= 8.72m

Approximate width of the plate = Height / No. of plates

=20/18 =1.11m

No. of plates = 18

Length of each plate = 8.72m.

Allowable stress S = 12.1 kgf/mm2 = 1210 kgf/cm2

D=50 m H= 20m E=0.85

Referring to IS code 803:1976, minimum nominal thickness for 50m diameter tank is
34.5mm.

For the 1stthickness section:

Thickness of the 1st shell course, t1 = 50(H-0.3)DG/SE

56
 = 50(20-0.3)*50*1/1210*0.85

= 47.88mm

Adding the corrosion allowance, t1 = (47.88+0.5)mm

= 48.38mm

Next higher standard value of thickness is 50mm.

For the second thickness section:

Thickness of 2nd shell course, t2 = 50(20-1.11-0.3)DG/SE

= 50(20-1.11-0.3)*50*1/1210*0.85

= 45.187mm

Adding corrosion allowance, t2 = (45.187+0.5)

= 45.68mm

Next higher standard value of thickness is 50mm.

For the third thickness section:

Thickness of the 3rd shell course, t3 = 50(H-0.3)DG/SE

= 50(20-(2*1.11)-0.3)*50*1/1210*0.85

= 42.48mm

Adding the corrosion allowance, t3 = (42.48+0.5)

=42.98 mm

Next higher standard value of thickness is 45mm.

For the fourth thickness section:

Thickness of 4th shell course,t4 =50(H-.3)DG/SE

=50(20-(3*1.11)-0.3)*50*1/1210*0.85=39.79mm

Adding the corrosion allowance,t4 =(39.79+0.5)

57
 = 40.29mm

Next higher standard value of thickness is =45mm

For the fifth thickness section :

Thickness of 5th shell course,t5 = 50(H-0.3)DG/SE

= 50(20-(4*1.11)-0.3)*50*1/1210*0.85

= 37.09mm

Adding the corrosion allowance,t5 = (37.09+0.5)

= 37.59mm

Next higher standard value of thickness is =40mm

Thickness of 6th shell course,t6 = 50(H-0.3)DG/SE

=50(20-(5*1.11)-0.3)*50*1/1210*0.85

=34.39

Adding the corrosion allowance,t6 = (34.39+.5)=34.89

Next higher standard value of thickness is =36mm

Thickness of 7th shell course,t7 = 50(H-0.3)DG/SE

=50(20-(6*1.11)-0.3)*50*1/1210*0.85

= 31.69mm

Adding the corrosion allowance,t7 = (31.69+.5)=32.19

Next higher standard value of thickness is =36mm

Thickness of 8th shell course,t8 = 50(H-0.3)DG/SE

=50(20-(7*1.11)-0.3)*50*1/1210*0.85

=28.99mm

Adding the corrosion allowance,t8 =(28.99+0.5)=29.49

58
Next higher standard value of thickness is =36mm

Since the nominal thickness has to be 34.5mm. So, the 9th-18th shell plates will be of
34.5mm

H=20MM

505045

D = 22m
THICKNESS OF SHELL PLATES

59
4.2. DESIGN OF HEAT EXCHANGER:

It is required to design a Heat Exchanger (cooler) to cool a stream coming from the
ammonia synthesis reactor, comprising of Ammonia( NH3), Nitrogen(N2),
Hydrogen(H2) and Argon(Ar). The stream is to be cooled from450ºC to50ºCby using
water available at 30ºCand leaving at 90ºC .

Let,Inlet temp.of gas steam = 450°C = 842°F

Outlet temp.of gas stream = 50°C = 122°F

Inlet temp.of water = 30°C = 86°F

Outlet temp.of water = 90°C = 194°F

Flow rate of water = 123665kg

N2 = 80068kg

H2 = 17158kg

Ar = 456kg

NH3 = 41667kg

Total = 139349

Mass flow rate of the gas = 139349 kg/hr = 306935.68 lb/hr

4.2.1. DETERMINATION OF CALORIC TEMPERATURE:

(T2-t1) =(122-86)°F = 36°F

At cold temp.difference, viscosities are found out.

µwater = 1cp

4.2.2. VISCOSITIES OF THE GAS MIXTURE:

µN2 = 0.0175 cp

µH2= 0.0085cp

60
µAr = 0.022cp

µNH3 = 0 .01cp

4.2.3. MASS FRACTIONS:

XN2 = 0.572

XH2= 0 .126

XAr= 0 .003

XNH3= 0.297

Viscosity of gas mixture = (µN2. XN2 + µH2. XH2 + µAr. XAr + µNH3.XNH3)

= 0.0141cp

Since the viscosity of the gas mixture at the cold terminal temperature difference is
less than, hence the mixture is non viscous and its variation of viscosity with temp. is
negligible. So for evaluation of properties of the gas stream, we consider the average
temperature. Again the viscosity of water at the cold terminal temperature difference
is so we take the average temperature.

Average temp of gas stream Tavg = 482°F

Average temp of water stream, tavg = 140°F

4.2.4. PROPERTIES OF THE GAS STREAM AT:

(i) Thermal conductivity(K) : (Btu/hr.ft °F)

N2 = 0.024
H2 = 0.0165
Ar =0 .01
NH3 = 0.0269

Thermal conductivity of gas mixture, Kmix = 0.0428

(ii) Specific heat (Cp) : (Btu/lb°F)

N2 = 0.2
H2 = 3.42

61
 NH3 = 0.52
Ar = 0.12

Specific Heat of the gas mixture, Cpmix = 0 .7287

(iii) Viscosity (µ) : cp

N2 = 0.0265
H2 = 0.0128
NH3 = 0.018
Ar = 0 .034

Viscosity of the gas mixture, µmix = 0.022*2.42 = 0 .053

4.2.5. PROPERTIES OF WATER :

Kwater = 0.383Btu/hr.ft°F

µwater = 0.47*2.42 = 1.137cp

Cp = 1Btu/lb°F

4.2.6. CALCULATION OF LMTD:

LMTD = [(T1-t2) – (T2-t1)]/ ln[(T1-t2)/(T2-t1)]

= [(842-194)-(122-86)]/ln 648/36

= 211.76°F

R = T1-T2/t2-t1

= 6.67

S = t2-t1/T1-t1

= 0.1428

FT =0.90 (fig 18 of Kern’s “process heat transfer”)

Corrected LMTD =211.76*.90 = 190.584°F

62
4.2.7. ASSUMPTIONS:

1) We consider the exchanger to be a 1-2 shell-and-tube exchanger.

2) The assumption is based on the values of overall heat transfer coefficient.
While selecting a value of overall design coefficient from a given range, it is
normally selected towards the higher range because it decreases the surface
area equipment.

For gas water system, from table 8 of Kern’s “ Process Heat Transfer”, we get
the range of overall design coefficient to be 2-50 at a dirt factor of 0.003.

Let, UD = 50 Btu/ft2.hr°F

Now Q = UDA∆T

A = 1648 ft2

4.2.8. ASSUMPTIONS IN DESIGNING THE HEAT EXCHANGER:

1)(a) Tubes of ¾” OD and 16 BWG are considered.

(b) Length of each tube is 16ft long.

(c) Tubes are laid on 1” sq pitch.

2) A combined dirt factor .003 is considered.

A = 1700 ft2

Surface area available for single tube =πDoL

where, Do = Outer Diameter

L = Length of tube

Surface area available for single tube=π*0.75/12*16 = 3.14ft2

No.of tubes required = 525 tubes

Referring to page 841, table 9 of Kern’s “Process Heat Transfer”, we find that for 1”
sq.pitch

63
No.of tubes = 526

Shell ID =31”

4.2.9. DIMENSION OF THE HEAT EXCHANGER:

SHELL SIDE TUBE SIDE

No.of pass = 1 No.of pass = 2

Shell ID = 31” No.of tubes = 526

Baffle Spacing = 6.2” Length of tubes = 16ft

OD of tubes = ¾”, 16BWG

ID of tubes = .620”

Pitch = 1”(square)

In case of Heat Exchanger design, if one of the fluids is corrosive, then it is always
passed through the tube side of a Shell and Tube Heat Exchanger. If neither of the
fluids is corrosive, then the larger flow rate stream is passed through the larger flow
area side and the smaller flow rate stream is passed through the smaller area side. In
this case, since water is corrosive, we take water in tube side and gas mixture in shell
side.

4.2.10. FLOW AREA CALCULATIONS:

4.2.10.1. TUBE SIDE:

Referring table 10, page 843 of Kern’s “Process Heat Transfer”,

Flow area of each tube = 0.302in2

Tube side flow area, at = Flow area of each tube*( no.of tubes/no. of passes)

64
=(.302/12*12)*526/2

= 0.551ft2

4.2.10.2. SHELL SIDE:

For square pitch,

Clearance, C = PT – Dio = 1- ¾” = 0.25”

Baffle Spacing = 6.2”

Shell side flow area = ID*C*B/144*P = 0.33ft2

4.2.11. CALCULATION OF LOCAL HEAT TRANSFER

COEFFICIENT:

TUBE SIDE(Water,cold) SHELL SIDE(Gas,hot)

(i) Reynolds no., (i) Re = Di,G* GG/µmix

Re = DVᵨ/µ GG = mass vel.of gas mix
Gw = Mass vel. of water = mass flow rate/area
= Mass flow rate/area = 139349*.454/.33

= 1500510.8/.5= 93598.25 lb/ft2.hr = 191710442.42 lb/ft2hr

= 2728201.45 Re = 139514.3745

Re = 1491609.

De = 4[ PT2-∏Dio2/4]∏Di

, = 4[1-π*.752/4]π*.75
= 0.079

Velocity through tube,

V = Gw/3600ᵨ

65
 (ii) hi = 440*.95 = 418 Btu/ft2 hr°F (ii) Prandtl no. = Cpµ/L = 0 .9023
(iii) hio = hi(Ai/Ao) (iii) Referring fig 28 of page 838 of = hi
(Di-Do) Kern’sProcess Heat Transfer

= 418*.620/.75 jH = 230

= 345.54 Btu/hr.ft2°F (iv) ho = jH(Kmix/De) (Pr)1/3 (µ/µw).14

=230* (.0428/.079)*(.9023)1/3

= 120 Btu/ft2.hr°F

(iv) Clean overall coefficient Uc

Uc = ( hohi)/(hi+ho)
= 345.54*120/345.54 +120
=89.06 Btu/hr.ft2°F
(v) Design Overall Coefficient UD
Q = UD * A * ∆T
A = 526*16*.1963 = 1652.06 ft2

∆T = 190.584°F

UD = 51.46 Btu/hr.ft2°F

(vi) Dirt factor, Rd :

Rd = Uc – UD/ UC*UD
= 89.06 – 51.46/ 89.06*51.46
= .008

66
4.2.12. PRESSURE DROP CALCULATION :

SHELL SIDE TUBE SIDE

(i) “Process Heat Transfer”For Re = 1491609.2 Tube side friction factor, f =.0025

For Re = 935982.5

Shell Side friction factor, f= .0014

(ii) No.of crosses, N+1 = 12L/B (ii)∆P=fGt2

ln/5.22*1010*Ds*Φt

r =12*16/6.2 = 0.0025*(272820)2*16*2/5.22

=30.96*1010*0.62/12*1=
0.22psi

(iii) Ps= fGs2Ds(N+1)/5.22* 1010*De*S*Φs (iii) At Gt = 272820, v2/2g

= 0.009

=0 .0014*30.96*(306935.68)2*2.58/5.22* (Refer fig 27,page 837 of Kern)

1010*.079*.8*1)

=0.03 psi (iv) ∆Pr = 4 n/s (v2/2g)

67
=4*2/1(0.009)=0.072 psi

(v) Total pressure drop,

∆PT = ∆Pt + ∆Pr

=0.22 +0.22 =0.292 psi

CONCLUSION

The Haber process produces 100 million tons of nitrogen fertilizer per year, mostly in
the form of anhydrous ammonia, ammonium nitrate and urea.1% of the world’s
annual energy supply is consumed in the Haber process. That fertilizer is responsible
for sustaining 40% of the Earth’s population, as well as various deleterious
environmental consequences, although the total may be higher due to the North
Korea’s refusal to give reports.

On the blessing side synthetic nitrogen fertilizer produced by the Haber process is
credited with feeding a third to half the present world population. In fact about half
the nitrogen in each of our bodies is there thank to the Haber process. On the curse
side we have several issues including:

 Serious imbalances to the nitrogen cycle.

 High fossil fuel energy inputs.
 Negative impacts on soil organisms and soil organic matter.
 Excess runoff cause ocean dead zones.
 Major component of weapons including all those roadside bombs.

Overall, ammonia is highly used and is harmful to a certain extent. It is in humans and
animals, and the reactants that are used to produce ammonia are present in the air that
we breathe. However, when directly exposed as a gas in a different way, than
naturally, it can be nothing but deadly, and highly dangerous. The chemical formula
for ammonia, is a result of mixing hydrogen and nitrogen, to produce ammonia. It has
a reversible reaction, and is an endothermic reaction. It is a closed system equilibrium.

68
REFERENCES

1. Narayanan K.V. and Lakshmikutty B., Stoichiometry and Process Calculations

PHI Learning Private Limited, New Delhi,2009.
2. Kern Donald Q., Process Heat Transfer, McGraw Hill Education (India) Private
Limited, Edition 1997, New Delhi.
3. Perry Robert H. and Green Don W.,Perry’s Chemical Engineers Handbook,8th
Edition, The McGraw Hill Companies.
4. http://www.chemguide.co.uk/physical/equiliria/haber.html
5. http://www.easychem.com.au/monitoring-and-mangement/maximising-
production/history-of-the-haber-process

69