8/20/15

LECTURE16:
NITRIC ACID AND UREA

CHEMICAL TECHNOLOGY (CH-206)

Department of Chemical Engineering

AMMONIA
8/20/15

Ammonia (NH3) or azane is a compound of

nitrogen and hydrogen.
It is a colourless gas with a characteristic
pungent smell.
Ammonia contributes significantly to the
nutritional needs of terrestrial organisms by
serving as a precursor to food and fertilizers.
Ammonia is both caustic and hazardous.

AMMONIA: PROPERTIES
Properties
NH3

Molar mass

17.031 g/mol

Appearance

Colourless gas

Odor

strong pungent odor

Density

0.86kg/m3(1.013 bar at boiling point)

0.769 kg/m3(STP)
0.73kg/m3(1.013 bar at 15C)
681.9kg/m3at 33.3C (liquid)
817kg/m3at 80C (transparent solid)

Melting point

77.73C (107.91F; 195.42K)

Boiling point

33.34C (28.01F; 239.81K)

Solubilityinwater

47% w/w (0C), 31% w/w (25C), 18% w/w (50C)

Solubility

soluble inchloroform,ether,ethanol,methanol

Vapor pressure

8573 h Pa

Acidity(pKa)

32.5 (33C)

8/20/15

Molecular formula

AMMONIA: PROCESSES
8/20/15

Haber Bosch process

Modified Haber Bosch process
Killogg ammonia process

AMMONIA: HABER AND BOSCH

PROCESS
Raw materials
Basis:

8/20/15

1000kg of NH3 (85% yield)

Hydrogen

210kg (synthesis gas)

Nitrogen
960kg (air or air liquefaction
process)
Catalyst
0.2kg
Power
850KWH
Fuel gas for compressors 3800Kcal
Cooling water
12,500kg

AMMONIA: HABER AND BOSCH

PROCESS

Raw material sources:

it is taken form air as discussed

Hydrogen It can be synthesized from any feed
stock listed below:

8/20/15

Nitrogen

Feed stock

Process or techniques to produce H2

Natural gas

Partial oxidation / steam reforming

Coke oven gas

Partial oxidation/ low temperature

separation

Fuel oil or low sulfur heavy stock

Partial oxidation

Coal

Partial oxidation

Water

Eletrolysis
6

AMMONIA: HABER AND BOSCH

PROCESS
Catalyst

8/20/15

Iron

with added promoters e.g. oxides of aluminium,

zirconium or silicon at about 3% concentration and
potassium oxide at about 1%.
Promoters prevent sintering and make the catalyst more
porous.
Iron catalysts lose their activity rapidly, if heated above
520C.
Also, is deactivated by contact with copper, phosphorous,
arsenic, sulfur and CO.

AMMONIA: HABER AND BOSCH

PROCESS
8/20/15

Purification of raw gases

AMMONIA: HABER AND BOSCH

PROCESS
Purification of raw gases

liquid nitrogen wash is mainly used to purify and

prepare ammonia synthesis gas within fertilizer
plants.
The liquid nitrogen wash has the function to remove
residual impurities like CO, Ar and CH4 from a crude
hydrogen stream and to establish a stoichiometric
ratio H2/N2 = 3:1.
CO must be completely removed, since it is poisonous
for the NH3 synthesis catalyst.
Ar and CH4 are inert components enriching in the
ammonia synthesis loop. If not removed, a syngas
purge or expenditures for purge gas separation are
required.

8/20/15

The

AMMONIA: HABER AND BOSCH

PROCESS
Purification of raw gases
If

partial oxidation of coal, heavy oil or residue oil

were selected as feedstock basis for ammonia
production then liquid nitrogen wash is typically
arranged to downstream of the scrubbing process.
Traces of water, CO, solvent (methanol) are removed
in the adsorber station.
Center piece of the liquid nitrogen wash is referred as
coldbox.
The process equipment of the cryogenic separation is
installed close-packed in the coldbox, which is covered
with a metal shell.
The coldbox voidage is filled with insulation material
(perlite) to prevent heat input.

8/20/15

10

AMMONIA: HABER AND BOSCH

PROCESS
8/20/15

Raw hydrogen and HP nitrogen are fed to the

liquid nitrogen wash unit.
Both streams are cooled down against product
gas.
Feeding raw hydrogen to the bottom of the
nitrogen wash column and some beforehand
condensed liquid to the top.
Trace components are removed and separated as
fuel gas.
To establish the desired H /N ratio, HP nitrogen
2
2
is additionally admixing inside and outside the
coldbox.

11

AMMONIA: HABER AND BOSCH PROCESS

(1910)
Ammonia is manufactured by passing mixture of
pure H2 and N2 in the proportion of 3:1 by volume
under pressure (1001000 atm depending on
conversion required).

8/20/15

Reaction
N2(g) + 3H2(g) 2NH3(g) H = 22.0 kcals

12

AMMONIA: HABER AND BOSCH PROCESS

8/20/15

13

Ammonia converter: Carbon steel (CS) is used as material of construction

(MOC) for pressure vessel and internal tubes.

AMMONIA: HABER AND BOSCH

PROCESS
8/20/15

N2 and H2 are first passed through filter to

remove compression oil and additionally through
a high temperature guard converter (convert CO
and CO2 into CH4 and remove traces of H2O, H2S,
P and As).
The relatively cool gas is added along the outside
of converter tube walls to provide cooling.
The preheated gas flows next through the inside
of the tube which contains promoted iron catalyst
at 500-550 0C.

14

AMMONIA: HABER AND BOSCH

PROCESS
The NH3 product, with 8-30% conversion
depending on a process conditions, is removed by
condensation, first with water cooling and then
NH3 refrigeration.

8/20/15

The unconverted N2H2 mixture is recirculated to

allow an 85-90% yield.
Economy of the process is greatly influenced by
the pressure, temperature, catalyst, purity of raw
materials and most importantly heat recovery
and reuse.

15

AMMONIA: MODIFIED HABERBOSCH

PROCESS

The NH3 is also manufactured by the partial

oxidation of hydrocarbon derived from naphtha,
natural gas or coal by oxygen enriched air in the
presence of catalyst.

8/20/15

Modified Haber Bosch process has following steps

Manufacture
Purification

of reactant gases

Compression
Catalytic

reaction
Recovery of ammonia and recycle of reactant gases

16

AMMONIA: HABER AND BOSCH PROCESS

(1910)
8/20/15

Reaction
N2(g) + 3H2(g) 2NH3(g) H = 22.0 kcals

17

8/20/15

AMMONIA:
HABER AND
BOSCH
PROCESS

18

Ammonia converter: Carbon steel (CS) is used as material of construction

(MOC) for pressure vessel and internal tubes.

AMMONIA: MODIFIED HABERBOSCH

PROCESS
MANUFACTURE OF REACTANT GASES

Producer gas is prepared by passing air through heated

coke or coal bed at100014000C.
Resulting CO2 passed through the hot bed of the fuel which
reduced it to CO, the nitrogen of the air remains mixed
with CO.
The gas is cooled and purified.
In both the cases sensible heat of the gases is utilized by
raising steam in waste heat boiler
C + 1/2O2 CO
H = 28900 cal

8/20/15

Water gas as source of H2 is prepared from coke and steam

at 1000 14000C.
It is cooled and purified by passing through lime and iron
oxide coated wood shavings.
C + H2O CO + H2 H = 38900 cal

19

AMMONIA: MODIFIED HABERBOSCH PROCESS

PURIFICATION

8/20/15

Both water and producer gases are mixed in such a ratio so that
after purification concentration of N2 and H2 by volume becomes
1:3.
The cold mixed gas is mixed with excess steam, then the hot gases
are passed through horizontal converters containing catalyst
consisting of iron oxide promoted with Cr2O3 and CeO2.

The CO is converted into CO2 by steam at 4500C temperature by

the heat of reaction.
CO + H2 + H2O CO2 + 2H2O H = 98,000 cals.

The hot mixture of CO2, H2, N2 and CO is cooled by passing

through the heat exchanger then the cooled gas is stored.
The gases, after removal of CO 2, are compressed to 200 atm
pressure, cooled, and treated in a pressure tower with ammonical
solution of cuprous formate (HCOOCu) which absorbs CO.
The resultant gas is mixture of H 2 and N2 (3:1).

20

AMMONIA: MODIFIED HABERBOSCH

PROCESS
COMPRESSION

8/20/15

The purified N2 and H2 mixture at 200 atm

pressure is further compressed to 300atm pressure
mixed with recycling gas at the same pressure and
passed through oil filters.
The compressed gas mixture is then cooled by cold
water followed by refrigeration by liquid ammonia.
The recycling gas in the mixed gas contained some
ammonia.
This ammonia is liquefied by pressure and
refrigeration hence before allowing the gas
mixture to enter into the converter, the liquid
ammonia is separated.

21

AMMONIA: MODIFIED HABERBOSCH PROCESS

CATALYTIC REACTION

8/20/15

The gas mixture then passes into the converter which is

made of Ni, V, Cr steel having 7 height and 21
diameter.
The seamless cap having 3 wall thickness is held by
bolts of nickel steel.
The converter is fitted with double coil acting as heat
exchanger through the inner tube of which cold gas
mixture passes, and through the outer tube of which
passes the hot outgoing gas mixture.
At the base of the coil there is resistance coil for
electrical heating.
In the converter there is the contact catalyst chamber
consist of three concentric tubes which contain the
granular catalyst.

22

AMMONIA: MODIFIED HABERBOSCH PROCESS

CATALYTIC REACTION

8/20/15

The compressed gas enters through the inner coil

of the heat interchanger.
After passing through the interchanger the gas is
heated electrically by the resistance coil and then
goes up 1st catalyst chamber, and then down
through the 2nd, and lastly up through the last.
It then enters the outer coil of the central heat
exchanger, gives up the heat to the incoming gas,
and then goes out of the converter from the top.
The temperature in the contact chamber is
5500C.

23

AMMONIA: MODIFIED HABERBOSCH PROCESS

RECOVERY OF NH3 AND RECYCLE OF REACTANT GASES

8/20/15

The mixed outgoing gas containing 19% NH3 and

rest N2 and H2 going out of the converter is cooled
by cold water in the condenser, where major
portion of ammonia liquefies.
The liquid NH3 is separated and the unconverted
gas mixture containing some unliquefied NH3 is
compressed to 300atm pressure and then mixed
with fresh compressed gas mixture and recycled.
A part of the recycled gas is rejected from time to
time to prevent the accumulation of argon and
methane.

24

AMMONIA: KILLOGG AMMONIA

PROCESS
Raw material
Natural
Air

gas

8/20/15

Reaction
2CH4 + O2 2CO + 4H2
2CO + O2 2CO2
N2 + 3H2 2NH3
25

AMMONIA: KILLOGG AMMONIA

PROCESS
8/20/15

Natural gas is used for production of hydrogen.

The purified nitrogen and hydrogen is reacted to give ammonia gas.

26

AMMONIA: KILLOGG AMMONIA

PROCESS
8/20/15

27

AMMONIA: KILLOGG AMMONIA

PROCESS

The exit gas containing poison was regenerated in the

methanator at 280-3500C which ultimately used for
heating the feed water.

8/20/15

The sulfur free natural gas is mixed with steam in the

volume based ratio of 3.7:1 and compressed to 40 atm.
The mixture is preheated with the recycled flue or
effluent gases and fed into the furnace.
At 800-8500C in the presence of iron catalyst promoted
with other metal oxides conversion of methane takes
place with the formation of CO.
The residual gas is mixed with air and fed into shaft
converter to get complete conversion.
The waste heat is utilized for the steam generation and
ethanolamine which are used in CO2 and H2S removal.

28

AMMONIA: KILLOGG AMMONIA

PROCESS
Purified N2 and H2 mixture was compressed to
300atm at 320 to 3800C in the presence of
catalyst converted to NH3.

8/20/15

14-20% conversion per pass was achieved.

NH condensed and separated from exit gas,
3
whereas unconverted N2 and H2 gases were
recycled along with the fresh gases.
Ammonia synthesis is being exothermic the
process requires an effective temperature control
system at every stage of reaction.

29

AMMONIA: PROCESS DESIGN

MODIFICATIONS

The various process used with different process parameter are

as follows

8/20/15

The pressure affects conversion, recirculation rates and

refrigeration of the process.

Very high pressure (900-1000atm, 500-6000C, 40-80% conversion)

Claude, Du pont, Lair liquide
High pressure (600atm, 5000C, 15-25% conversion) Casale
Moderate pressure (200-300atm, 500-5500C, 10-30% conversion)
Haber Bosch, Kellogg, Fauser, Nitrogen Engineering Corporation
Low pressure (100atm, 400-4250C, 8-20% conversion)
Mont Cenis: uses a new type of iron catalyst promoted iron cyanide.

The modern trend is towards lower pressure and increased recirculation

loads because of the relatively high cost of pressure vessels.
The large single train plants using centrifugal compressors and having
capacities as high as 1000 tons/day from a single reactor at low
production cost are used widely.

30

AMMONIA:
USES

Ammonia

is major raw material for fertilizer

8/20/15

industries
It is used for the manufacture of

Nitro compounds, Fertilizers e.g. urea, ammonium sulfate,

ammonium phosphate etc.
Nitric acid, Hydroxylamine, Hydrazine, Amines and
amides, and in many other organic compounds

It

is also used in heat treating, paper pulping, as

explosives and refrigerants

31

NITRIC ACID: INTRODUCTION

8/20/15

Nitric acid (HNO3) is also known as aqua fortis

(strong water) and spirit of niter.
It is a highly corrosive strong mineral acid.
Commercially available nitric acid having
concentration of 68% HNO3, while the solution
containing more than 86% HNO3, is referred to
as fuming nitric acid.

Depending

on the amount of nitrogen dioxide

present, fuming nitric acid is further characterized as
white fuming nitric acid or red fuming nitric acid, at
concentrations above 95%.
32

NITRIC ACID: TIMELINE

8/20/15

First reference of Nitric acid is mentioned in PseudoGeber's De Inventione Veritatis which is prepared by
calcining a mixture of saltpetre (Niter KNO3), alum
and sulfuric acid.
In 13th century Albertus and Ramon Lull prepared
HNO3 by heating niter and clay and called as "eau
forte" (aqua fortis).
Glauber invent the process to obtain HNO 3 by
heating niter with strong sulfuric acid.
In 1776, Lavoisier showed that it contained oxygen.
In 1785, Henry Cavendish determined its precise
composition and synthesized it by passing a stream of
electric sparks through moist air.

33

NITRIC ACID: MANUFACTURING

PROCESSES
Nitric acid is manufactured by three methods.
Chile

saltpetre or nitrate
Arc process or Birkeland and Eyde process
Ostwald's process or Ammonia oxidation process

8/20/15

34

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS

Nitric acid is made by the oxidation of ammonia,

using platinum or platinum- 10% rhodium as
catalyst, followed by the reaction of the resulting
nitrogen oxides with water.

8/20/15

Raw Materials
Basis:

1 t nitric acid (100%)

Ammonia 290kg (from Haber Bosch process)
Air
3000 Nm3
Platinum 0.001 kg (catalyst)
Water 120000 kg
Steam
1000 kg @ 200psig
Power 1030 KWH

35

NITRIC ACID: MANUFACTURING

PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION

PROCESS
8/20/15

Reaction:
Major reactions
4NH3 + 5O2 4NO + 6H2O H = - 216.6 kcals (1)

2NO+O2 2NO2

H = - 27.1 kcals

Side reactions
4NH3 + 3O2 2N2 + 6H2O

(2)

H = - 302.7kcals (3)

2NH3 N2 + 3H2 H = + 26.7 kcals (4)

2NH3 + 2O2 N2O + 3H2O

H = - 65.9kcals

(5)

4NH3 + 6NO 5N2 + 6H2O + 432.25 kcal H = - 431.9kcals

(6)

Nitrous oxide oxidation and absorption

2NO+O2 2NO2 H = - 27.1kcals (7)
3NO2 + H2O 2HNO3+ NO
2NO2 N2O4

H = - 32.2kcals

H = - 13.9kcals

2NO2 + H2O HNO3 + HNO2

(8)

(9)

H = - 27.7kcals(10)

HNO2 H2O + NO + NO2 - (11)

36

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
The process involves four steps
1.
2.
3.
4.

Catalytic oxidation of ammonia with atmospheric

oxygen to yield nitrogen monoxide
Oxidation of the nitrogen monoxide product to
nitrogen dioxide or dinitrogen tetroxide
Absorption of the nitrogen oxides to yield nitric acid
Concentration of nitric acid

8/20/15

37

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
8/20/15

38

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION PROCESS

8/20/15

39

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
8/20/15

Compressed air is mixed with anhydrous

ammonia, fed to a shell and tube convertor
designed so that the preheater and steam heat
recovery boiler-super heater are within the same
reactor shell.
The convertor section consists of 10-30 sheets of
Pt-Rh alloy in the form of 60-80 mesh wire gauge
packed in layers inside the tube.
Contact time of the gas passes downward in the
catalyst zone 2.5 104 sec and are heated at
8000C.

40

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
8/20/15

Product gases from the reactor which contain 10-12%

NO, are sent through heat recovery units consisting of
heat recovery boiler, super heater and quenching unit
for rapid cooling to remove large fraction of product
heat, and into the oxidizer-absorber system.
Air is added to convert NO to NO 2 at the more
favourable temperature (40-500C) environment of the
absorption system.
The equipment in the absorption train may be series of
packed or sieve tray vertical towers or a series of
horizontal cascade absorbers.
The product from this water absorption system is 5760% HNO3 solution which can be sold as or concentrated
further.

41

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
Concentration by H2SO4
Rectification

with 93% H2SO4 (660Be) in silicon-iron or

stoneware tower produces concentrated nitric acid and
70% H2SO4 which can be re-evaporated to 93% H2SO4 or
used as it is.

8/20/15

Concentration by Mg(NO3)2
Magnesium

nitrate solution (70-75% Mg(NO3)2) is fed to

dehydrating tray along with dilute HNO3 from the
Advantages
absorption tower.
Operating cost is half compare to H2SO4 process

The salt solution acts as an extractive distillation agent,
Acid quality and yield improved
removing water at 1000C or higher, thus allowing
rectification with azeotropic formation.
Disadvantage
The dilute
Mg(NO
solution re-concentrated by

Increase
in 70%
capital3)2expenditure
evaporation

42

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
ENGINEERING ASPECTS
Thermodynamics and kinetics
4NH3 + 3O2 2N2 + 6H2O H = 302.64 kcal (12)

8/20/15

4NH3 + 6NO 5N2 + 6H2O H = 432.25 kcal (13)

2NO N2 + O2 H = 43 kcal

(14)

All the above exothermic reaction takes place in more or less

extent.
Reactions 12 and 13 occurs with decrease in enthalpy with
increase in number of moles followed by increase in entropy.
Ammonia oxidation reaction has an extremely favourable
equilibrium constant so that one step, high temperature
converter design may be used.
43
4NH3 + 5O2 4NO + 6H2O

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
Following condition should be fulfilled to convert
NH3 into NO

limit: The explosion limits are avoided by

employing quantity of air such that the amount of
ammonia mixed with it is less than 10.5 vol% of total
volume.
Thermodynamics: The thermodynamics of competing
reactions (12) and (13) are rendered unfavourable by
working above 5000C, while the reaction (14) are not
favoured if the process is carried out under 12000C
Kinetics: Kinetics of reaction (1) is speeded up by use of
catalyst. This is also done by preventing any reduction in
the velocity of the reaction brought about by presence of
inert gas nitrogen in the reaction zone.

8/20/15

Explosion

44

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
Reaction kinetics in ammonia oxidation stage
Rate

of reaction is directly proportional to system pressure

Alloying of platinum with rhodium improves yield at given
There
is slight equilibrium advantage to operation at atmospheric
set
of
pressure.conditions
This is more than offset by increased capacity in a given
Reaction
to form
NO is favoured
by increasing
reactor
volume
with subsequent
catalyst
and reactortemperature
savings when
until anhigh
optimum
is reached
which increases with higher
operating
pressures
(3-8atm.)
Oxidation
of nitrogen
oxideinto
doesthe
notprevention
have large of
equilibrium
constant.
velocities.
This results
back diffusion
Therefore,
thehigher
reaction
predominates
in water
andIfabsorption
of NO into
NH
region.
this occursportions
3 concentration
0
of the
which
operates
at low
temperature
at 4050
the process,
following
reaction
is quite
probable
and should
be C. All the
nitrogen
oxide
liberated
on absorption of NO2 must be reoxidized in
avoided
for high
NO yield.
absorption tower

8/20/15

4NH3 + 6NO 5N2 + 6H2O

Rate

of NO formation very nearly corresponds to diffusional

transport of ammonia molecules to the catalyst surface
45

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS

of abortion depends on concentration of NO2 in

gas phase. In absorber where concentration of NO2 is
greater than 5%, the controlling reaction is solution
of N2O4 accompanied by hydrolysis of HNO3 and
HNO2.
Low temperature is beneficial for absorber operation
efficiency
Increasing pressure favours physical absorption rate
and shift chemical equilibrium to produce higher acid
strength

8/20/15

Absorption of nitrogen oxides into water

Following design criteria should be considered

Rate

46

NITRIC ACID: MANUFACTURING PROCESSES

OSTWALD'S PROCESS OR AMMONIA OXIDATION
PROCESS
8/20/15

Process design modification

Most plants operate at higher pressure (3-8atm) rather than
complete atmospheric pressure. Some operates at a combination
of 1atm pressure oxidation and high pressure absorption. Very
high pressure is limited due to cost of pressure vessel.
Advantages and disadvantages of elevated pressure are as
follows

Advantages

Higher acid strength

Lower investment cost
Higher reaction rate and lower volume in both oxidation and absorption
equipment

Disadvantages

Lower oxidation yield

Higher power require if recovery units are not specified
Higher catalyst loss unless good catalyst recovery procedure are not used

47

NITRIC ACID: PROPERTIES

Physical Properties
Molecular

8/20/15

formula : HNO3
Molecular weight :
63.013 gm/mole
Appearance : Colourless liquid
Odour :
Pungent
Boiling point : 1210C (68% HNO3 solution)
Melting point :
420C
Density : 1.5129 gm/mL (liquid)
Solubility :
Miscible with water in all proportions
The impure nitric acid is yellow due to dissolved oxides of nitrogen, mainly NO 2.
It has a corrosive action on skin and causes painful blisters.

Chemical Properties
Acidic

properties: It is a strong monobasic acid and ionization in aqueous

solution.
Oxidizing properties: It acts as a powerful oxidizing agent, due to the formation
of nascent oxygen.
Action on metals: It reacts with almost all the metals, except noble metals, like
Pt and Au. The metals are oxidized to their corresponding positive metal ions
while HNO3 is reduced to NO, NO2. N2O, NH2OH or NH3, depending upon the
conditions such as temperature, nature of metal and concentration of the acid.
Nitric acid has ability to separate gold and silver.

48

NITRIC ACID: APPLICATIONS

As a raw material in the manufacture of
nitrogen

fertilizers such as ammonium nitrate, ammonium

phosphate and nitrophosphate.
adipic acid.
fibers, plastics and dyestuffs industries,
metallurgy and in rocket fuel production,
organic intermediates such as nitroalkanes and
nitroaromatics.

Weak acid are used to digest crude phosphates.

As a nitrating agent in the preparation of explosives
such as TNT, nitroglycerine, cellulose polynitrate,
ammonium picrate
As the replacement of sulfuric acid in acidulation of
phosphate rock.

8/20/15

49

UREA: INTRODUCTION
Urea (NH2CONH2) or carbamide is an organic compound has
two NH2 groups joined by a carbonyl (C=O) functional group.

Urea serves an important role in the metabolism of nitrogen

containing compounds by animals and is the main nitrogen
containing substance in the urine of mammals.
Urea has the highest nitrogen content available in a solid
fertilizer (46%).
Urea is easy to produce as prills or granules and can be easily
transported in bulk or bags with no explosive hazard.
Urea dissolves readily in water. It leaves no salt residue after
use on crops and can often be used for foliar feeding.
Urea can be sprayed on leaves and can also be mixed with
insecticides or herbicides for soil application.
Urea ammonium nitrate mixture with herbicide is also used for
weed control.

8/20/15

50

UREA: INTRODUCTION
8/20/15

When applied to a bare soil surface, urea hydrolyzes rapidly

result into loss of significant quantity of ammonia by
volatilization. Such losses vary from soil to soil and are
greater for urea in a pellet form rather than in solution
form.
It is phytotoxic due to rapid hydrolysis of urea in soils can
cause injury to the seedlings by ammonia,
The fertilizer grade urea may contain toxic biuret which is
formed during urea manufacture by an excessive
temperature rise. Above 2% concentration of biuret in urea
is harmful to plants.
Feed grade urea is sometimes referred by the number 262
which is the product of its nitrogen content (42%)
multiplied by 6.25, the latter being the factor used by
chemists to convert nitrogen to its protein equivalent.

51

UREA: TIMELINE
8/20/15

Herman Boerhaave was first who discovered urea

in urine in 1727, however this discovery is often
credited to Hilaire Rouelle.
In 1828, Friedrich Whler synthesized urea from
an inorganic precursor.

It

was the first time that the molecule found in living

organisms could be synthesized in the laboratory
without biological starting materials.
Due to this discovery, Whler is considered as the
father of organic chemistry by many scientists.

52

UREA: MANUFACTURE PROCESS

Item
NH3 (Haber

Once Through
1150kg

8/20/15

Raw materials:
Basis: 1 t prilled urea
Partial recycle
880kg

Total Recycle
600kg

Bosch process)
CO2

1470kg

910kg

770kg

Power

210 kWH

165kWH

145kWH

Steam

1800kg

2000kg

2400kg

Cooling water
120000kg
70000kg
Reaction
CO2 + 2NH3 NH2COONH4
H = 37,021 Kcal
NH2COONH4 NH2CONH2 + H2O
H = +6.3 kcals

110000kg
53

UREA: MANUFACTURE PROCESSES

8/20/15

Block flow diagram for urea synthesis

14 Mpa,
170 190 OC

54

Process flow diagram for urea synthesis

UREA: MANUFACTURE PROCESSES

The reactor must be heated to force the reaction to proceed.

CO2 is introduced at process pressure followed by stripper.

8/20/15

Liquid ammonia, gaseous carbon dioxide and recycle

materials charged in the heat exchanger-reactor at the
pressure of 14MPs at 1701900C to form carbamate, with
most of the heat of reaction carried away as useful process
steam.
The carbamate decomposition reaction is both slow and
endothermic.
The mixture of unreacted reactants and carbamate flows to
the decomposer.
The stoichiometric ratio of CO 2/NH3 conversion to urea is
essentially about 55%, but by using an excess of CO 2 (or
NH3) the equilibrium can be driven as high as 85%.

55

UREA: MANUFACTURE PROCESSES

8/20/15

All the unreacted gases and undecomposed carbamate to

be removed from the product, the urea must be heated at
lower pressure (400kPa).
The reagents are reacted and pumped back into the
system.
Evaporation and prilling or granulating produces the
final product.
Overall, over 99% of both CO2 and NH3 are converted to
urea, making environmental problems to minimum.
Carbamate is highly corrosive to both ordinary and
stainless steel, but with oxygen present, 300 series
stainless steel resist it very well, so some air is
introduced along with CO2 reagent to reduce system
corrosion.

56

UREA: MANUFACTURE PROCESSES

8/20/15

Developments in urea process technologies

Component

Unit

Process
Montedison's

TEC-ACES

Stamicarbon

Ammonia

IDR process

process

stripping

casale's

process

SRR
process

Ammonia

kg

570

570

570

570

CO2

kg

740

740

740

740

Steam

kg

900

800

660

790

Power

KWH

140

140

16

21

Water

m3

3.1

2.4

3.1

3.0

57

UREA: MANUFACTURE PROCESSES

MONTEDISON'S IDR PROCESS

8/20/15

Montedison's process employing two specially

designed stripping columns.
Ammonia and CO2 are used as the stripping agent in
1st and 2nd column, respectively.
The reactor constructed in two sections having
perforated trays and also a down comer meant for
circulation solution.
High NH3 to CO2 ratio results in increased
conversion efficiency and lower carbamate recycle
duty of the plant.
Excess NH3 is removed by CO2 stripping instead of
distillation as practiced in conventional total recycle
processes, minimizing the energy requirement.

58

UREA: MANUFACTURE PROCESSES

TEC ACES PROCESS

8/20/15

This is typically CO2 stripping process employing

higher ratio (4:1) of NH3 to CO2, and higher
synthesis pressure leading to high conversion
efficiencies as compare to total recycle process.
Stripping is carried out in a two stage stripper
constructed of special steel.
The upper part of the stripper is a tray column
for the removal of excess ammonia whereas the
lower part is a falling film exchanger for the
stripping action.

59

UREA: MANUFACTURE PROCESSES

STAMICARBON STRIPPING PROCESS

Consumption of steam is decreased by employing

a

pool condenser of new design featuring high

resistance time,
direct heat exchange between condensing vapours
from stripper and the stripped urea solution; and
an evaporator of improved design which allows better
utilization of multiple effect principle in heat
transfer.

8/20/15

60

UREA: MANUFACTURE PROCESSES

AMMONIA CASALE'S SRR PROCESS

8/20/15

Split reaction recycle (SRR) process of ammonia

casale is based on stripping technology of either
snamprogetti or stamicarbon and includes
installation of secondary high pressure section
consisting of feed pump, reactor, supplementary
decomposer and separator which extend the urea
formation reaction.
The operating conditions are same as traditional
ones.
The new secondary section added to the synthesis
loop can be pre-fabricated on skid mounted units
and can be erected at site without any modification
on the layout of the existing synthesis section.

61

UREA: MANUFACTURE PROCESSES

GRANULATION

granulation and falling curtain granulation

process of Tennessee Valley Authority (TVA)
High temperature pan granulation (GTPG) process of
Norsk Hydro.
Fluidized bed granulation process of Hydro Agri
Licensing & Engineering.
Fluidized bed granulation process of TEC.

8/20/15

Granular urea minimize air pollution and

granules has higher strength larger sizes and is
more compatible with other granular fertilizers.
Following commercial processes are available for
granulation of urea:

Pan

62

UREA: MAJOR ENGINEERING

PROBLEMS
AUTOCLAVE VARIABLES

The objective of autoclave reaction is to produce the optimum

economic yield. The conditions which affects rate of reactions are
temperature, pressure, NH3/CO2 ratio and feed rate.

8/20/15

The urea production rate can be varied as follows

Increase

with increasing pressure

Increase with temperature to maximum at 175180 0C, then falls of
sharply. The operating pressure should be above the dissociation
pressure (dissociation pressure is 180 atm at 190 C) for the carbamate.
Use no excess ammonia.

Reasons for not operating at maximum temperature and pressure

without excess ammonia
Increased

pressure increases capital and operating cost of compression

and reaction equipment.
At higher temperature urea decomposed to biuret, which is detrimental
to germinating seeds and toxic to animals.
63
The above process conditions enhance corrosion rates to machinery

UREA: MAJOR ENGINEERING PROBLEMS

CARBAMATE DECOMPOSITION AND RECYCLE

8/20/15

It is optimized by short residence times in a stripping

column operating at low pressure and high temperature.
Later should be below 110 0C if hold up time exceeds 1-2
seconds to avoid biuret formation.
Use of millisecond contact time in a flash evaporator allows
1400C operating temperatures in the high recycle design.
Main difference in competing processes is in the recycle
design.
Since conversion is only 40-50% per pass, the unreacted off
gases must be recirculated or used economically elsewhere.
Recompression of off gases is virtually impossible because of
corrosion and formation of solid carbamate in compressors.
A solution is formed and pumped into the autoclave.

64

UREA: MAJOR ENGINEERING

PROBLEMS
Production of granular urea (Prilling)

It may result into biuret formation.

Vacuum drying of 80% urea to > 99% and spraying to air cooled and
solidify must be done just above the melting point of urea and with a
minimum residence time.

Heat dissipation in the autoclave

8/20/15

The exothermic heat of reaction can be removed by coils, wall cooling,

or by adding excess reactant to provide sensible heat pick up.

Corrosion

It can be minimized by use of the corrosion resistant metals and

maintaining the proper reaction conditions.
High cost silver or tantalum liners are used in the autoclaves with
titanium, stainless (321SS) and aluminum alloys used in other parts of
the plant.
Minimum temperature and pressure with excess NH 3 are desirable to 65
reduce the severe corrosion rates.

UREA: PROPERTIES
Molecular formula : CH4N2O

Molecular weight :

60.06gm/mole

Appearance :

White granules

Odour :

Bulk density :

Angle of repose : 300

Melting point :

1321350C

Density :

1.32 gm/ml

Solubility :

Solubile in water, ethanol, glycerol

Moisture :

1% by wt. (Max.)

8/20/15

Odourless
673-721 kg/m3

Dissolved in water, it is neither acidic nor alkaline.

As soon as urea dissolves in the soil, it forms around it a zoning
layer of high pH and ammonia concentration turning the soil to be
acidic and toxic at the same level.

66

UREA: APPLICATIONS
8/20/15

As a fertilizer
As a protein food supplements for ruminant
As an ingredient in the manufacture of resins,
plastics, adhesive, coatings
Textiles anti-shrink agents and ion exchange
resins
In melamine production
It is an intermediate in the manufacture of
ammonium sulfamate, sulfamic acid and
pthalocyanines.

67

ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin

G. T., "Shreves Chemical Process Industries",

Fifth edition, Tata McGraw Hill, NY.
Kent J.A., "Riegel's Handbook of Industrial
Chemistry, CBS Publishers.
Gopala Rao M. & Marshall Sittig, "Drydens Outlines of
Chemical Technology for the 21st Century", Affiliated
East West Press, New Delhi.
Mall I. D., "Petrochemical Process Technology",
Macmillan India Ltd., New Delhi.
http://nptel.ac.in/courses/103106108/24

8/20/15

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