COLLEGE OF ENGINEERING

Department of Mechanical and Industrial

Engineering

CHEMICAL PROCESS TECHNOLOGY (EME20303)

FALL SEMESTER (2023-24)
CHAPTER 5
Nitrogen Industry
 What’s Inside?

1 Introduction (Video Clips)

;;

2 Synthesis of Ammonia

3 Manufacture of Nitric Acid

4 Manufacture of Urea

4 Self test / Formative Quiz

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Introduction (Video clips)
https://www.youtube.com/watch?v=9qpgDfZKmxc

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Synthesis of Ammonia

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Process Description
1) Ammonia synthesis gas (3 moles pure H2 : 1 mol pure N2) is compressed to the
operating pressure (100-1000 atm depending on conversion required).
2) It is sent through a filter to remove compression oil and additionally through a high
temperature guard converter (converts CO and CO2 to CH4 and removes traces of H2O,
H2S, P and As.
3) The relatively cool gas is added along outside of the converter tube walls to provide
cooling so that carbon steel can be used for the thick wall pressure vessel and internal
tubes.
4) The preheated gas next flows through the inside of the tubes, which contain promoted
porous iron catalyst at 500-550 deg C.
5) The NH3 product with an 8-30% conversion depending on process conditions is removed
by condensation, first with water-cooling and then NH3 refrigeration.
6) The unconverted N2-H2 mixture is recirculated to allow an 85-90% yield.

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Ammonia and Its Properties
Ammonia (NH3)
❑ a compound of nitrogen and hydrogen.
❑It is easily liquefied due to the strong hydrogen bonding between molecules

Haber Process
❑combines nitrogen from the air with hydrogen derived mainly from
natural gas (methane) into ammonia.
❑The reaction is reversible and the production of ammonia is exothermic.
❑The mixture of nitrogen and hydrogen going into the reactor is in the
ratio of 1 volume of nitrogen to 3 volumes of hydrogen

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 PFD of Nitric Acid Manufacturing

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Process Description
❑ Compressed air is mixed with anhydrous ammonia (90% and 10% respectively).

❑ It is fed to a shell and tube converter designed so that the preheater and a steam heat recovery boiler and
superheater are within the same reactor shell.

❑ The pressurized mixture is passed over catalyst gauze of 90% platinum and 10% rhodium.

❑ Product gases from the reactor containing 10-12% NO are sent through heat recovery units, a quench unit
for rapid cooling to remove a large fraction of the product heat and into the oxidizer-absorber system.

❑ Air is added to convert NO to NO2 at the more favourable low temperature (40 – 50 °C) environment of the
absorption system.

❑ The product from the water absorption system is 57-60% HNO3 which can be sold as it is or concentrated to
the desired strength.

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

ProdUse of Catalyst Recovery Filter
uction of Nitric Acid
As ammonia and air are
burned at the platinum
catalyst gauze within the
converter vessel, a gradual
catalyst breakdown occurs
and the catalyst dust is carried
downstream and is captured
in the catalyst recovery filter.
 Ostwald Process: Reactions involved
NOTE: The critical step in nitric acid production, the catalytic combustion of ammonia, was developed by Ostwald around
the turn of the century and was in production by 1906.

1) Catalytic oxidation of Ammonia :

➢ Ammonia reacts with oxygen in the air to form nitrogen monoxide and steam.
➢ This is an oxidation reaction. A catalyst of hot platinum metal is used to increase the rate of reaction.
(Platinum is an expensive metal so platinum gauze is used - giving a large surface area for a relatively small amount of
metal.)

4NH3 + 5O2 → 4NO + 6H2O ΔH = - 900 kJ/mol

2) Oxidation of Nitrogen monoxide (NO)

2NO + O2 → 2NO2 ΔH = - 115 kJ/mol

2NO2 ↔ N2O4 ΔH = - 58 kJ/mol

3) Dinitrogen Tetroxide Absorption

3N2O4 + 2H2O → 4HNO3 + 2NO ΔH = - 103 kJ/mol

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Urea and its Raw Materials
➢ Urea is now prepared commercially in vast amounts from liquid ammonia and
liquid carbon dioxide.
➢ These two materials are combined under high pressures and elevated
temperatures to form ammonium carbamate, which then decomposes at much
lower pressures to yield urea and water.
➢ The raw materials which are used in urea manufacturing process are ammonia
and carbon dioxide hence generally urea is manufactured in an ammonia plant
because it yields ammonia as a product and carbon dioxide as a byproduct
➢ The carbon dioxide can be used directly for manufacturing urea

Fall Semester
(2023-24) EME20303 Chemical Process Technology (BEngCHE)
 Uses of Urea
Urea is used in the production of:
❑ pharmaceuticals,
❑ resins,
❑ aviation fuel and lubricating oils,
❑ solid fertilizer
❑ Liquid fertilizer
Other applications such as:
❑ animal feed,
❑ adhesives.
Urea-formaldehyde resins
❑ have large use as a plywood adhesive.

Melamine-formaldehyde resins
❑ used as dinnerware.
❑ Melamine is synthesized by condensation of urea molecules.

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Manufacture of Urea

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Process Description
❑ Liquid ammonia is pumped and carbon dioxide is compressed and transported to an equipment called reaction
chamber. Since this is were the reaction happens, it is the heart of the process. The pressure and temperature is
maintained at 14 Mpa and 170-190°C for the first reaction to occur. The reaction of ammonia and carbon dioxide is
highly exothermic in nature. Most of the heat released is utilized in the form of process steam wherever it is needed to
process
❑ The product from the first reaction flow into a decomposer where the second reaction occurs and it is an endothermic
reaction. It requires certain energy to begin. Biuret is also formed as a result of decomposition of ammonium
carbamate if temperature rise is excessive.
❑ The conversion of the reactants to urea can be increased by increasing the amount of carbon dioxide, if carbon dioxide
is present in excess then the conversion can be as high as 85% per pass but optimizing for the proper temperature,
pressure and design is a challenge in itself hence usually per pass conversion are kept around 50%. The unreacted
materials are recycled resulting in overall conversion of over 99%. This minimises the effects on environment.
❑ The major impurity in urea is water and also unreacted ammonia, carbon dioxide and ammonium carbamate. These
are removed using distillation tower and evaporator. Essential condition is to keep temperature high and pressure low
during stages of separation. At these conditions the ammonium carbamate will be decomposed back to ammonia and
carbon dioxide also some carbon dioxide and ammonia will flash off. The major process which happens in the
evaporator is that of concentration. During concentration optimum temperature should be maintained so that the urea
remains in molten state and crystals are not formed inside the evaporator.
❑ The molten urea is passed through nozzles inside the prilling tower. Compressed air is passed in the tower so that its
flow is counter current with respect to that of molten urea. The urea gets solidified in the prilling tower and air helps in
shaping it in the form of prills or granules. The urea is then stored and ready to be sold.

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Reactions involved
Two chemical reactions are primarily involved in the process. Both reactions are
reversible

(1) Reaction of Ammonia and Carbon Dioxide to form Ammonium Carbamate

2NH3 + CO2 → NH2COONH4

(2) Decomposition of Ammonium Carbonate to form Urea and Water.

NH2COONH4 → H2O + NH2CONH2 (urea)

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Example# 5.1
In the manufacture of nitric acid, pure dry sodium nitrate is treated with 95% (weight) sulphuric acid.

Acid is supplied in excess to ensure that the resulting nitre cake is liquid containing 35%
sulphuric acid by weight. The cake contains 1.5% water by weight. In addition 2% of the nitric
acid formed will remain with the cake. For a basis of 100 kg of sodium nitrate treated,
calculate the following:

(a) The weight and composition of the nitre cake

(b) The weight of sulphuric acid to be used
(c) The weight of nitric acid product obtained
(d) The water vapour that is distilled from the nitre cake,

Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)

 Prepared by: Sonia Ibarra Buscano (Course Coordinator)
Fall Semester (2023-24) EME20303 Chemical Process Technology (BEngCHE)