KMM 412E CHEMICAL TECHNOLOGIES 1

LECTURE 6. Synthesis of Ammonia and Urea

02/11/2015

Prof.Dr. Hale GRBZ

 INTRODUCTION
Ammonia is a major product of the chemical industry .
At present, about 85% of ammonia production is used for
nitrogen fertilizers. Direct application of ammonia represents
the largest single consumption (about 30%).
Urea is the most important solid fertilizer, accounting for
about 40% of ammonia usage. Other solid nitrogen fertilizers
are ammonium nitrate, ammonium sulfate, and ammonium
phosphates
Industrial applications of ammonia include the production of
amines (e.g. H3C-NH2, (H3C)2-NH), nitriles (e.g. acrylonitrile:
CH2=CH-C=N), and organic nitrogen compounds for use as
intermediates in the fine chemicals industry.
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Ammonia becomes increasingly important in environmental 2

applications, such as removal of NOx from flue gases of power
plants [1].
 INTRODUCTION
The Industrial Revolution and the related growth of the
population generated a large demand for nitrogen fertilizers.
In the beginning of this century, ammonia was produced as
by-product in coke ovens and gas works.
In these industries, ammonia is formed during the distillation
of coal. This source of ammonia is no longer important today.
During the start of the 20th century it was recognized that
supplies were not sufficient for agricultural needs. Moreover,
the explosives industry was developing into a large volume
industry due to the beginning of the First World War.
Therefore, the direct synthesis of ammonia from N2 in the air
was attempted. However, nitrogen is very stable and inert and
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it causes the difficulty in the synthesis of ammonia [1]. 3

 Ammonia synthesis was the first large-scale synthesis in the
chemical industry at high pressure ( > 100 bar) and high
temperature (670-870 K).
The reaction to be carried out is:

However, during the first attempts for ammonia synthesis

precise thermodynamic data were not known (where the
equilibrium is located at the conditions at which attempts to
synthesize ammonia were made).
Around 1910 it was shown that at atmospheric pressure in a
mixture of nitrogen, hydrogen, and ammonia hardly any NH3
is present [1].
Haber found that at 1290 K the fraction of NH3 in an
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equilibrium mixture of N2, H2, and NH3 (N2:H2 = 1:3)

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was only 0.01%.
 Meanwhile, more reliable thermodynamic data became
available. Haber extrapolated these data to lower
temperatures, and thus concluded that an industrial process
was feasible, if suitable catalysts could be developed.
Haber also pointed out that an industrial process is possible
even if conversion is not complete. He proposed a recycle
loop under pressure and also suggested the use of a feed-
effluent heat exchanger. These concepts are still the basis of
modern ammonia synthesis plants.
In a short period of 5 years (1908-1913) Haber developed a
commercial process in operation (30 t/d) in co-operation with
BASF.
The group at BASF tested over 6500 catalysts and discovered
that an iron based catalyst exhibits superior catalytic activity
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[1]. 5
 Ammonia production has grown exponentially, although
especially in Europe saturation has become visible [1].

Figure 6.1 Growth of ammonia production (left) and plant capacity (right) [1]

Capacities of modern plants are high. Although single-stream

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plants of over 2000 t/d are feasible, such large projects are
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more difficult to finance and are likely to encounter
constraints of feedstock availability and market [1].
 The production of ammonia requires a mixture of H2 and N2
in a ratio of 3:1.
The source of nitrogen is invariably air, but hydrogen can be
produced from a variety of fossil fuels.
Steam reforming of natural gas followed by autothermic
reforming with air is most often employed in ammonia plants
and accounts for approximately 80% of ammonia production
[1].
Thermodynamics
Figure 6.2 shows the ammonia equilibrium content in
equilibrium synthesis gas as a function of temperature and
pressure.
The favorable conditions for ammonia synthesis are low
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temperature and high pressure [1] 7

 kinetic limitations exist:
at temperatures below
about 670 K the rate of
reaction is very low.
Therefore, a minimum
temperature is required
Regarding pressure the
optimal situation is a
compromise between
thermodynamically
favorable conditions and
minimum investment.

Figure 6.2 Ammonia content (mol%) in

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equilibrium synthesis gas; H2/N2 = 3 mol/mol;

based on data from [1] 8
 Ammonia Synthesis Reactors:
Temperature control is crucial in ammonia synthesis: the reaction
is exothermic and the heat produced needs to be removed. Two
methods are applied:
Quench reactors: cold feed gas is added at different heights in
the reactor
Heat exchangers between the catalyst beds: The heat
produced is removed by heat exchangers. Hence, heat is
recovered at the highest possible temperature.

Part of the cold feed is introduced

at the top and passes downward
between the catalyst-filled
section and the converter shell,
thus maintaining the shell at
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relatively low temperature.

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ICI: Imperial Chemical Industries Ltd.

Figure 6.3 ICI quench reactor and temperature-concentration profile [1]
 Ammonia Synthesis Reactors:
Another quench reactor is the Kellogg vertical quench converter.
The Kellogg vertical reactor
consists of four beds held on
separate grids. Quench-gas
distributors are placed in the
spaces between the beds.
Kellogg has also
designed a hori-
zontal converter, for
plant capacities in
excess of 1700 t/d

Figure 6.4 Kellogg vertical (left) and Kellogg horizontal

quench reactor [1]
The feed enters the reactor at the bottom and flows upward between
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the catalyst bed and shell to be heated in a feed-effluent exchanger

located at the top of the vessel. The product gas outlet is also located at 10

the top.
 Ammonia Synthesis Reactors:
It is attractive to apply as small catalyst particles as possible to
increase the efficiency of the catalyst.
Of course, the pressure drop is a point of concern.
In a reactor designed by Haldor Topse two annular catalyst beds
are applied and the gas flows radially. This results in a lower
pressure drop.
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Figure 6.5 Haldor Topse radial-flow reactor [1]

 Ammonia Synthesis Reactors:
In the second type of reactor the catalyst bed is cooled by heat
exchangers. The cooling medium can be the reactant gas or steam
can be generated. These indirectly cooled reactor is preferred
when heat is to be recovered at high temperature [1].
A disadvantage is that the
investment cost is higher due
to the cost of the intermittent
heat exchangers.
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Figure 6.6 Multi-bed converter with indirect cooling; (a) catalyst, (b) feed-
effluent heat exchanger, (c) cooling section, (d) feed, (e) cold bypass, (f) product [1]
 Integrated Ammonia Plant:
Modern ammonia plants are 'single-train' plants (All major
equipment and machinery are single units).
The advantages: lower investments and simplicity.
The disadvantage: failure of a unit leads to plant shut down.
Fortunately, modern equipment is very reliable, and on-stream
factors of over 90% are common [1].
Ammonia production
capacity is generally
standardized to a
production of 1360 t/d.
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Figure 6.7 Flow scheme of an integrated ammonia plant [1]

 Syngas Plant for Ammonia:
After desulfurization the natural gas is fed to the steam reformer
(or primary reformer), where part of the feed is converted.

In the autothermic reformer (also referred to as the secondary

reformer), air, containing the required amount of nitrogen for
ammonia synthesis is introduced.

The secondary reformer operates at a temperature between 1100

and 1270 K and a pressure close to that of the primary reformer,
about 30 bar. The catalyst is similar to that employed in the
primary reformer (i.e. a supported nickel catalyst).
Carbon oxides are highly poisonous to the ammonia synthesis
catalyst. Therefore, the reformed gas is shifted and scrubbed for
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CO2 removal. 14
 The synthesis
gas then is
compressed
and
converted in
the ammonia
synthesis
reactor.
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Syngas Production Ammonia Production

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Figure 6.7 Flow scheme of an integrated ammonia plant [1]

 Table 6.1 Stream summary table of Figure 6.7 (Integrated ammonia plant) [1]
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 Production of urea
Urea is produced by reacting ammonia and carbon dioxide.
Carbon dioxide is obtained as a by-product of the ammonia
production process.
Reactions and thermodynamics
The formation of urea occurs through two uncatalyzed
equilibrium reactions[1]:
The first reaction: the formation of ammonium carbamate

Ammonium carbamate is liquid at reaction conditions, solid at standard temperature and

pressure
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The second reaction: the formation of urea

 Since more heat is produced in the first reaction than is
consumed in the second reaction, the overall reaction is
exothermic.
The most important side reaction is the formation of biuret:

Biuret is detrimental to crops even at very low concentrations,

so its formation should be minimized [1]

QUESTION:
What is the influence of temperature and pressure on the three reactions?
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 Thermodynamically, both CO2 conversion and the urea yield as
a function of temperature go through a maximum.(It is
dependent on the initial composition, but usually lies between
450 and 480 K at practical conditions).
QUESTION: Why do the CO2 conversion and the urea concentration go through
a maximum as a function of temperature?
Why does the presence of water have a negative effect on conversion and
urea yield?
Why is the urea yield not maximum at the stoichiometric NH/CO2 ratio but
somewhat above it?

Increasing the NH3/CO2 ratio gives a higher CO2 conversion (but

a lower NH3 conversion). The yield on urea has a maximum at a
NH3/CO2 ratio of somewhat above the stoichiometric ratio (2:1).
A large excess of ammonia results in a reduced yield (which is
defined as mole urea produced per mole feed).
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Water has a negative effect on the conversion of ammonia and
carbon dioxide and consequently on urea yield [1].
 From a kinetic viewpoint, both the carbamate forming reaction
and the urea forming reaction proceed faster with increasing
temperature. The carbamate-to-urea conversion is much slower
than carbamate formation
Temperatures of over 420 K are required for a sufficiently high
reaction rate. At these temperatures, pressures of over 130 bar
are required to prevent dissociation of ammonium carbamate
into ammonia and carbon dioxide(the reverse of reaction of
carbamate formation)
No catalyst is used because of the corrosiveness of the reaction
mixture, which would result in too many technical difficulties
with respect to catalyst stability.
At economically and technically feasible conditions, the
conversion to urea is only between 50 and 75% the reactor
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effluent will always contain a considerable amount of20

carbamate, so a separation step is necessary [1].
 In the separation of urea from the unconverted carbamate the
high rate of reaction (2) presents an opportunity for process
simplification.
Upon reducing the pressure of the reactor effluent (by flashing
through an expansion valve), the carbamate will decompose
to yield the initial reactants [1].
The remaining liquid phase is a urea solution containing up to
80 wt% urea.
Urea is rather stable and if the residence time at a high
temperature is sufficiently short, urea will not hydrolyze to form
carbamate.
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 The key challenge in the design of a urea plant is efficient handling of the
gases from the carbamate decomposition stage
Urea production processes may be divided in two groups:
once-through processes (the unconverted reactants were used in
downstream processes, for instance in the production of ammonium nitrate
and nitric acid)
total recycle processes.
The first commercial urea processes were once-through
processes Major disadvantage
of this type of plant
is that the econo-
mics of the plant are
not only dependent
on the market of the
main product(urea)
but also on that of
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the byproducts, such

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as ammonium
nitrate and nitric
Figure 6.8 Once-through process for urea production [1] acid
 Figure 6.8 Once-through process for urea production [1]
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 In total recycle processes no by-products are produced.

Figure 6.9 Total recycle process for urea production - recycle of separated NH3
and C02 [1]
However, recycling of the NH3/CO2 mixture is not as
straightforward as it may seem.
Recompression to reaction pressure is required result in the
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recombination of NH3 and CO2 to form liquid carbamate (or solid

carbamate at lower temperature) Normal compressors cannot 24

handle gases containing droplets or crystalsSOLUTION?

 1. SOLUTION: To separate the gases and recycle them separately.
Separation of NH3 and CO2 by scrubbing with a selective solvent
(Acid solvents like NH4NO3 selectively absorb ammonia, while
alkaline solvents such as aqueous amines (e.g. MEA and DEA) )
selectively absorb CO2. Figure 6.9 shows a block diagram of a
process in which ammonia is selectively absorbed.
2. SOLUTION: To condense the gases and recycle them in the
liquid phase.
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