Ammonia Production Mitul Parikh

From Natural Gas Assistant Professor

Haldor Topsoe Process Chemical Engineering
Department
 AMMONIA UREA
PLANT PLANT
Four
Sections
STEAM
BAGGING
GENRATION
PLANT
PLANT
 1 Desulphurization
2 Reforming
Ammonia section section

Plant 3 Shift section 4 Carbon dioxide

removal section
(900MT/Day)
5 Methanation
section
6 Ammonia
synthesis section
 Desulphurization Section

General Information:
• Natural gas contains up to 10
vol ppm sulphur compounds. HTZ – 5 catalyst
• Gas contains both H₂S and
organic sulphur compounds. TK- 250
• Desulphurization takes place
in two stages.
1. Hydrogenation
2. H₂S absorption
 C2H6- 9
C3H8- 3
C4H10- 2
C6H12- 0.25
CH4 – 84.50
Hydrogenation
N2 – 1.25

35˚C
(39 Kg/cm2)

(38 Kg/cm2) (395˚C)

(400˚C)
HTZ – 51 catalyst
TK-250 must not get into CoMo or In case if Natural gas containing CO and
TK- 250 contact with HC’s NiMo based
without presence of CO₂ is fed to the hydrogenator, the
catalyst.
hydrogen. This will (Pyrophoric following reactons will take place
increase sulphur slip to ) CO₂ + H₂ ↔ CO + H₂O
reforming section.
CO₂ + H₂ ↔ COS + H₂O
(351˚C)
 C2H6- 9
C3H8- 3
C4H10- 2
C6H12- 0.25
CH4 – 84.50
H₂S absorption
N2 – 1.25

35˚C
• The hydrogenated natural gas is fed to
(39 Kg/cm2) the Sulphur Absorbers ( R 202 A/B).
• Zinc oxide catalyst is in the form of 4
Does not react with Oxygen and mm extrudates.
(38 Kg/cm2)
hydrogen, (395˚C)
Not pyrophoric. Steam
(400˚C) • Operating temperature is approx.
operation should not be carried out. HTZ – 51 catalyst
395˚C.
Operating temp – 350-400’C
ZnO = More than 95% ZnO + H₂S ↔ ZnS + H₂O
TK- 250
Al2O3 = Less than 5% ZnO + COS ↔ ZnS + CO₂
Shape- Cylindrical Extrudates
• Sulphur content in the natural gas =
less than 0.1 ppm by weight
(351˚C)
Ar – 0.02, CH4 – 79.68, CO – 2 ppm,
CO2 – 0.24, H2 – 4.09, N2 – 2.54,
C2H6 – 6.48, C3H8 – 2.63, C4H10 –
1.88, C6H12 - 0.24
 Reforming Section

General Information:
Desulphurized gas is converted into synthesis
gas by catalytic reforming of the hydrocarbon
mixture with steam and the addition of air.

CnH2n+2 + 2H₂O ↔ Cn-1H2n + CO₂ + 3H₂ - heat

CH₄ + 2H₂O ↔ CO₂ + 4H₂ - heat
CO₂ + H₂ ↔ CO + H₂O - heat

Reactions take place in two steps

1. Primary reforming
2. Secondary reforming
 Primary Reforming
• Heat is transferred by radiation from a number of
wall burners to the catalyst tubes.
Contents • Hydrocarbon in the feed converted to CO₂ and
Nickel(Ni) H₂ with 13.3 mole% of methane(dry)
Calcium Oxide(CaO)
520˚C Potassium oxide(K2O) • Reformer tubes is loaded with catalyst RK-211
RK-211 Aluminum Oxide(Al2O3 ) (prereduced) followed by a layer of RK-201,
while the bottom part of the reformer tubes is
Nickel Monoxide(NiO)
Calcium Oxide(CaO loaded with catalyst R-67_7H.
Potassium oxide(K2O) Operating parameter
RK-201 Aluminum Oxide(Al2O3 ) 1. Inlet temperature : 520 ºC
2. Exit temperature : 785 - 795 ºC
Nickel Monoxide(NiO) 3. Pressure: 34 - 31 kg/cm2 g
R-67_7H Calcium Oxide(CaO 4. Steam/carbon ratio: 3.0 mole/mole
Aluminum Oxide(Al2O3 ) Ni-S + H2O = NiO + H2S
C+O2 = CO2
791˚C
Composition : (Mole %) Composition: (Mole %)
(At Inlet of Catalyst (At Outlet of Catalyst
Tubes) Tubes)
Ar – 0.02 Ar – 47 ppm
CH4 – 79.68 CH4 – 12.86
CO – 2 ppm CO – 9.5
CO2 – 0.24 CO2 – 10.70
H2 – 4.09 H2 – 66.20
N2 – 2.54 N2 – 0.74
C2H6 – 6.48 Higher HC - Neglegible
C3H8 – 2.63
C4H10 – 1.88
C6H12 - 0.24

Primary Reformer Inlet & Outlet

 Ar – 47 ppm
CH4 – 12.86
Secondary Reforming CO – 9.5
CO2 – 10.70
H2 – 66.20
• The process gas is mixed with air. N2 – 0.74
(550 ˚C)
• Partial combustion takes place in the top
of R 203.
• Methane concentration is 0.60
mole%(dry).
520˚C (1100-1200˚C )
• Outlet gas contains about 13.05mole%
(dry) CO and 7.24mole% (dry) CO₂. RKS-2
NiO = 8 – 10%
• Loaded with RKS-2-7H, and RKS-2 Al2O3 = 87 – 90 % RKS-2-7H
catalyst. Cao = < 0.05
H2+O2=H2O RKS-2
CH4+O2= CO2+2H2O 958˚C
Operating Pressure: 30 kg/cm2 g
H2/N2 Ratio: 3.0
Ar – 0.27
CH4 – 0.60
791˚C CO – 13.37
CO2 – 7.65
H2 – 55.61
N2 – 22.47
 CO Shift Section

General Information:
CO + H2O ↔ H2 + CO2 + heat
• Shift reaction takes place in the two CO
converters:
• HT CO-Converter( R 204)
• LT CO- converter (R 205) with process gas
cooling after each converter
 Ar – 0.27, CH4 – 0.60,
CO – 13.37, CO2 – 7.65,
H2 – 55.61, N2 – 22.47 HT CO-Converter(R 204)
360˚C
(29.6 kg/cm2) • Contains SK-201-2 catalyst installed.
1. Mechanical stability • The catalyst is Cu promoted
2. Low Steam to Carbon ratio iron/chromium based, in the form of
(SK-201-2) 3. Low byproduct formation pellets.
Fe2O3 - 85- 95 % • Can operate continuously in the range of
Cr2O3 - 7-9 % 320-480˚C.
CuO - 1-2% • Chlorine and inorganic salts are poisons to
Al2O3 - 1.0% the catalyst. (Below 1ppm)

432˚C 205˚C

Ar – 0.24
CH4 – 0.55
CO – 3.22
340˚C
CO2 – 15.94
H2 – 59.59
N2 – 20.48
Ar – 0.27, CH4 – 0.60,
CO – 13.37, CO2 – 7.65,
H2 – 55.61, N2 – 22.47 LT CO-Converter(R 205)
360˚C (28.6 kg/cm2)
• (29.6
Consist of oxides of
kg/cm2) • Loaded with a top layer of LSK and a bottom
205˚C
copper, zinc, chromium or layer of LK-821-2.
aluminium
(LSK) • Can be operated within a temperature range
(SK-201-2) • Temperature range - 170-
of 170-250˚C.
250˚C.
• Top layer catches possible • The activity of the catalyst increases with
chlorine in the gas and also increasing temperature, but the life of the
preventsliqvid droplets from catalyst shortened
reaching bottom (LK-821-2) • LSK is installed to catch possible chlorine in
layer.(Disintegration may the gas.
takes place) • Amount of CO (3.22 – 0.30), CO2 (15.94 –
432˚C 205˚C 227˚C 160˚C 17.72)

Ar – 0.24 Ar – 0.24
CH4 – 0.55 CH4 – 0.53
CO – 3.22 CO – 0.30
340˚C CO2 – 18.32
CO2 – 15.94
H2 – 59.59 H2 – 60.73
N2 – 20.48 N2 – 19.88
 R3N + CO2 + H2O ↔ R3NH+ + HCO3-
2R2NH + CO2 ↔ R2NH2+ + R2N-COO-

CO2 Removal Section

General Information:
• Based on two stage activated
MDEA process
• The solvent used for CO2
absorption is aMDEA(40%)
• Consists of a two stage CO2
absorber, a CO2 stripper and
two flesh vessels.
• Outlet gas from CO
converter contain 17.7 mole%
CO2.
99.88% CO2
(50˚C) (72˚C) CH4, CO, CO2, H2, N2
(50˚C)
0.59 Kg/cm2 5.1 Kg/cm2
0.35 Kg/cm2
Ar- 0.29
Purified gas
26.7 Kg/cm2 CH4-
(60˚C) 0.65
(F-304 CO2 Stripper) (45˚C) (50˚C) CO- 0.36
IMTP-25 CO2-
Process gas (95˚C) 0.05
(160˚C)
27.8 Kg/cm2 H2- 74.29

IMTP-50
N2-
(76˚C) 24.36
IMTP-50
Ar- 0.24
Process gas (65˚C)
CH4- 0.53
27 Kg/cm2
CO- 0.30
(131˚C) (82˚C) CO2- 17.7
(65˚C) H2- 80.75
Process N2- 19.89
Condensate
(65˚C)
 Methanation Section

General Information:
• Methanation, a process in which the residual
corbon oxides are converted into methane.
• Methane acts as an inert in the ammonia
synthesis section
CO + 3H2 ↔ CH4 + H2O + heat
CO2 + 4H2 ↔ CH4 + 2H2O + heat
• Low temperature, high pressure and a low
water vapour content favours the
methanation equilibrium.
• Methanator (R 301) has one catalyst bed
loaded with PK-7R catalyst
 Ar- 0.29, CH4- 0.65,
CO2-0.05,CO-0.36,
• Temperature range of H2- 74.29,N2- 24.36
methanator- (280˚C - 420
• Now pressure of gas
˚C ) (300˚C) is increased from 25
to 187 Kg/cm2 in
• Catalyst sensitive to PK-7R various stages with
sulphur, chlorine
compounds. Synthesis gas
• PK-7R is Nikel based compressor, gas
catalyst. booster.
• At every stage
Deactivation of catalyst can be temperature gets
caused by: (285˚C) (322˚C) increases, to
(60˚C)
• Thermal ageing 26.7 Kg/cm2 maintain low
• Gradual poisoning by
temperature Syngas
impurities in the feed gas
compressor chillers
• CO
such& as
CO2potassium, sulphur
conc. Should be (100˚C)
or arsenic.
below 1 mole% to minimize
are installed in
temperature increment. between.
(90˚C)
25 Kg/cm2
Ar- 0.29, CH4- 1.08,
H2- 73.95, N2- 24.88
 187 Kg/cm2
Ammonia Synthesis Section
(130˚C)
General Information • Ammonia Synthesis catalyst -
• In ammonia converter R-501: KM1/KM1R
3H2 + N2 = 2NH3 + heat • Non
Highpyrophoric uptoof90-100’C
concentration oxygen
Temperature
compounds at range – 530-550’C
the converter
• High pressure and low
inlet, even for short periods of KM1/KM1R
temperature favours Features of the
time, should becatalyst :
equilibrium conc. of 1.Stable pressure drop
avoided.(permanent
ammonia. 2. Long operating
deactivation life
takesplace).
• About 20% of N2 and H2 is 3.High resistance to poison
converted to ammonia. Iron based catalyst with some
Features of the catalyst
• Unconverted remainder is non reducible oxides.
recycled back. temperature for 1. Stable pressure drop
• Normal operating
2. Long operating life
First bed : 370-510
Second bed: 425-480 3. High resistance to poison
Third bed: 420-460 (354˚C)
183.6 Kg/cm2
 Ar- 1.82, CH4- 6.18, H2- Ar- 2.49
65.95, N2- 21.99, CH4- 8.38
187 Kg/cm2 NH3- 4.06
(130˚C) H2- 82.48
N2- 20.82
NH3- 5.82

(10˚C) Ar- 3.16

178.9 Kg/cm2
Ar- 2.11 CH4- 16.12
CH4- 7.14 (270˚C) H2- 38.06
H2- 52.84 N2- 15.76
(180˚C)
N2- 17.61 (11˚C) NH3- 26.88
NH3- 20.30 (10˚C) 27 Kg/cm2
(354˚C)
(10˚C)

(12˚C)
25 Kg/cm2
Ar- 0.01
CH4- 0.16
H2- 0.06
N2- 0.04
NH3- 99.73
 Ar- 2.71
Ammonia Recovery 20 Kg/cm2 CH4- 9.46
(61˚C) H2- 65.73
N2- 22.08
NH3- 0.01

Ar- 2.49 Ar- 64ppm

CH4- 8.38 25 Kg/cm2 CH4- 0.03
H2- 82.48 H2- 0.06
178.9 Kg/cm2 N2- 0.02
N2- 20.82
NH3- 5.82 (10˚C) (45˚C) NH3- 99.88

Ar- 3.16 (11˚C)

CH4- 16.12 27 Kg/cm2
H2- 38.06
N2- 15.76
NH3- 26.88
(248˚C)
Thank you 