Ammonia and Urea synthesis

Dr. Salman Raza Naqvi

1
Ammonia & its application
Ammonia is one of the
most widely produced
chemicals in the world. It
is widely used in the
production of fertilisers,
cleaning products,
synthetic fibres,
explosives,
pharmaceuticals,
nitric acid and in the
treatment of effluent.

2
Ammonia Synthesis

3
Thermodynamics of Ammonia synthesis

 Reversible and exothermic reaction

 Nitrogen to Hydrogen is 1:3 ratio
 Temperature and Equilibrium Consideration
 Low temperature is favorable. Temperature as low as 400-450 0C
 At very low temperature, reaction become very slow. It is economical
for industry to wait for long time to get product.
 Temperature as low as 400-450 0C is a compromise to reach
equilibrium as soon as possible and conversion is around 15-18%
 High pressure is favorable. As it will increase the rate of collision of
molecules
 Pressure as high as 170-200 bar is used. Why this range of pressure?
 Cost incurred on producing and maintaining high pressure will
exceed the Cost of producing extra ammonia. So, this value of
pressure is an economical compromise.
 Catalyst speed up the reaction just. 4
 Ammonia content in equilibrium syngas
(H2/N2 = 3 mol/mol)

• Temperature : 675 K (inlet); 720–770 K (exit)

• Pressure : 100–250 bar

5
 Ammonia Synthesis
ZnO (Adsorption) & Co-
Mo (HYDRODESULPHERIZATION)
At 700K
Steam/ C ratio: 3:1
Ni catalyst, 700-1000 0C
Steam, reforming, water gas
shift reaction
Partial Oxidation, steam
reforming, water gas shift
reaction, Ni catalyst, Methane to
H2

http://www.gses.com/images/pressreleases/Manufacturing-Process- 6
Fertilizer.pdf
 Ammonia Process
• Ammonia is one of the most produced inorganic chemicals in the world (~180 Mn
ton / yr)
• Around 86% of global ammonia manufactured is used for fertilizer production
• Process was first commercialized by BASF (thru Haber Bosch process) in 1913,
large scale plants were introduced in 1960s, technology evolved and matured
thru 1970-90
• Most common raw-material is natural gas, followed by coal and naphtha
• Very challenging process (high T, high P, explosive, toxic mixtures)
• Complex technology involving multiple catalytic reactors, furnaces, compressors,
boilers, heat exchangers, refrigeration loop …. etc.

Renowned Commercial Processes Key Info.

• Haldor Topsoe, Denmark • 1 ton Urea needs 0.57 ton Ammonia
• Udhe (Thyssenkrupp), Germany • 1 ton Ammonia needs 7-10 Gcal (gas)
• Kellog Brown & Root, USA • 1 ton Ammonia costs ~300-450 $
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 Ammonia Plant
HP Steam Excess
Steam to
Urea Plant
Methane
(CH4)
G Carbon dioxide
(CO2)
Front Back
L
End End
Air G Syn. Gas Ammonia
(N2 , O2) (H2 , N2) (NH3)

Water
MP
(H2O)
Steam
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 Ammonia – Back
Front End
End

NATURAL RECYLCE
GAS H2 75%
AIR MP STEAM CO : 0.1%
CH4 70% N2 24% CARBON DIOXIDE 2
CO2 10% O2 21%
CH4 1%
N2 20% N2 79% LEAN
Ar traces
S 2–5ppm Ar traces SYN. GAS
H2 75%
HP STEAM
N2 24%
CH4 1%
Ar traces
W
H
B

WATER RICH

Comp. Purification 1o 2o HT/MT LT AGR Section Methanator

CO / CO2: ND
40 Reformer Reformer Shift Shift level
kg/cm2 S: < 5 ppb CH4: 8-10% CH4: 0.8-1.2% CO: < 1.5% CO: 0.2%

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 Purification Section
Endothermic Overall

RSH + H2 ↔ H2S + RH
CoMo / ZnO
ZnO + H2S → ZnS + H2O NiMo
350 – 49 Kg/cm2g
400°C

H2S < 5 ppm

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 Secondary Reformer
Nickel Catalyst
Exothermic
CH4 + 2O2 → CO2 + 2H2O

Combustion 2CH4 + 3O2 → 2CO + 4H2O

Primary Reformer 1200°C
Ni 2H2 + O2 → 2H2O
Nickel Catalyst
CH4 + H2O ↔ CO / CO2 + H2
Endothermic Ni
CH4 + H2O ↔ CO + ~ 900°C 33 Kg/cm2g
3H2 CH4 conc. 0.8 – 1.2 dry mol%
CH4 + 2H2O ↔ CO2
+ 4H2
CO2 + H2 ↔ CO +
H2O
800°C 34 Kg/cm2g
CH4 conc. 8 – 10 dry
mol% 11 of 34
Med. Temperature
Shift Conversion
Copper Catalyst
Exothermic Low Temperature
Cu Cu Shift Conversion
CO + H2O ↔ CO2 + H2
225°C 32 Kg/cm2g Copper Catalyst
CO conc. < 1.5 dry mol Exothermic
% CO + H2O ↔ CO2 + H2

200°C 31 Kg/cm2g

CO conc. < 0.2 dry mol%

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 ACID GAS REMOVAL
SECTION

Uses Hot Potash solution

30% K2CO3 + 1% Amine

activator

e.g. Benfield / Catacarb

process
Regenerator Absorber
0.5 Kg/cm2g 30 Kg/cm2g

CO2 > 99 dry CO2 < 0.1 dry

mol% mol %
K2CO3 + H2O + CO2 → 2KHCO3
2KHCO3 → K2CO3 + H2O + CO2

R3N + H2O + CO2 ↔ R3NH + HCO3-

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2R2NH + CO2 ↔ R2NH2+ + R2N-COO-
 Methanator

Nickel Catalyst
Ni
Exothermic

CO + 3H2 ↔ CH4 + H2O

CO2 + 4H2 ↔ CH4 + 2H2O

280°C 27 Kg/cm2g

CO / CO2 : ND level

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Ammonia – Back End
285oC
CIRCULATION GAS PURGE GAS
(to boilers)
Purge Gas Treatment
Ammonia Synthesis (Recovery of NH3 &
Fe H2)
Iron Catalyst
Exothermic

Recovered H2
Fe 3H2 + N2 ↔ 2NH3 AMMONIA REFRIGRATION LOOP

Recovered NH3
385°C 150-260
Kg/cm2g
32% conversion per
Fe pass
CIRCULATOR

BOILER PREHEAT COOLER CHILLER 1 CHILLER 2

450 C
o
360oC 75oC 40 C
o
15 C
o
-5oC

MAKEUP GAS
SYN. GAS UREA PLANT
H2 75%
LIQ. AMMONIA
N2 24%
CH4 1% • Conc. 99.8%
Ar traces • H2O < 0.2% STORAGE
 Urea Process
• Most popular fertilizer in the world (~90 Mn ton / yr). Around 90% of
the global urea production is used as nitrogenous fertilizer
• Urea was the first organic chemical to have been manufactured from
inorganic reactants in lab (Friedrich Wöhler, 1828). During 1940-70,
technology evolved from ‘once thru’ to ‘recycle process’ and eventually
morphed into ‘total recycle process’
• Currently, there are two main technologies (a) NH3 Stripping [Saipem],
(b) CO2 stripping [Stamicarbon / Toyo]. While both technologies
achieve similar energy efficiencies, there are major differences in
CAPEX, Operability, and Maintainability requirements
Renowned Commercial Processes Key Info.
• Saipem (Snamprogetti), Italy • 1 ton Urea contains 0.46 tons
• Stamicarbon, Netherlands Nitrogen
• Toyo Engineering, Japan • 1 ton Urea needs 5-7 Gcal (gas)
• 1 ton Urea costs ~200-300 $
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 Urea
• Ammonia and CO2 are fed into reactor at high temperature and
pressure
• Its 2-step process

• Unreacted Ammonia, CO2 and ammonia carbamate

• Ammonia carbamate is reduced to NH3 and CO2 and that
is recycled
• Biuret is a side reaction and that must be minimize
Once through Process
Total recycled Recycled loop
Stripping of NH3
Snam Progetti Process
Stamicarbon Process
 Urea Plant

Carbamate
NH3 L Decomposition
Evaporation

Synthesis Prilling /
L S Urea
H M Granulation
Vacuum
CO2 G P P P

Recovery of Recovery of
NH3 & CO2 Water

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 Urea Plant
CRBAMATE
CONDENSOR
NH3
WATER
RECEIVE NH
R 3
PCT SECTION

PRE.
SEPARATO LP CONC.
MP VACUU
R D
D M
STRIPPE
R

MP
M
ABSORBER
S BLS LS LS
+ LS
130 °C
190 °C MC 99.8%
33%
140 °C urea
urea 204 °C
REACTO 71%
R 44% urea
160 °C 130°C
urea
85%
• Round Prills
63%
urea • Size: 2-3 mm
urea
• Moisture:
0.30%
AI CO2 Synthesis Stripper MPD LPD Vacuum Prilling
R 155 kg/cm2g 145 kg/cm2g 17 kg/cm2g 4 kg/cm2g -0.7 kg/cm2g Atm
Carbamate: 2NH3 + CO2 ↔ NH2COONH4 Urea: NH2COONH4 ↔
NH2CONH2 + H2O
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 Urea synthesis
CARBON DIOXIDE

UREA MP LP
STRIPPER
REACTOR DECOMPOSER DECOMPOSER

AMMONIA

BAGGING & PRILL VACUUM PRE-

SHIPPING TOWER CONCENTRATOR CONCENTRATOR

DESPATCHABLE LIMITS
MOISTURE : 0.45%
BIURET : 1.00%
FINES : 3.50%
Prilled Urea Granular Urea
Review

27
 UREA MANUFACTURING PROCESS
AIR STEAM
NAT. GAS AMMONIA PLANT
CO2
FRONT-END
SEPARATION
BACK-END

RAW WATER
TW / CANAL

CARBON DIOXIDE

AMMONIA
AMMONIA
POWER STORAGE
STEAM TANK
UTILITIES COOLING WATER
TREATED WATER

BULK
UREA PLANT STORAGE

BAGGING
WASTE WATER
PLANT

ROAD RAIL
 AMMONIA PROCESS
STEAM AIR
NATURAL GAS

SULPHUR PRIMARY SECONDARY SHIFT

REMOVAL REFORMING REFORMING CONVERSION

AMMONIA CO2
TO UREA TO UREA

AMMONIA AMMONIA CO2

METHANATOR
SEPARATION SYNTHESIS REMOVAL
 UREA PROCESS
CARBON DIOXIDE

UREA MP LP
STRIPPER
REACTOR DECOMPOSER DECOMPOSER

AMMONIA

BAGGING & PRILL VACUUM PRE-

SHIPPING TOWER CONCENTRATOR CONCENTRATOR

DESPATCHABLE LIMITS
MOISTURE : 0.45%
BIURET : 1.00%
FINES : 3.50%
 CANAL WATER
UTILITIES PROCESS

DEMINERALI -
RESERVIOR CLARIFIICATION FILTRATION
ZATION

WELL WATER C. TOWER

PLANTS BBD

WASTE WATER FROM

PLANTS
POWER &STEAM
SCARP / E.PONDS BOILERS
GENERATION

CHROMATE REMOVAL
CANAL