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Introduction
Ammonia (NH3) is a compound of nitrogen
and hydrogen. It is a colorless gas with a
characteristic pungent smell of 'wet nappies'
this is because urine can decompose to
ammonia.
Year
2005
148
2006
153
2007
159
2008
158
2009
158
2010
159
Others
35%
America
11%
India
9%
Pakistan
1%
Russia
11%
Uses
Ammonia is major raw material for fertilizer
industries
It is used during the manufacture of Nitro
compounds, Fertilizers e.g. urea, ammonium
sulfate, ammonium phosphate etc.
It is also used in manufacture of Nitric acid,
Hydroxylamine, Hydrazine, Amines and
amides, and in many other organic
compounds
Uses
20% is used in
manufacturing:
Plastics
Synthetic fibres
Explosives
Dyes
Pharmaceuticals
Industrial refrigerant
Industrial and domestic
cleaning agent
History
Gaseous ammonia was first isolated by Joseph Priestley in 1774 and was
termed as "alkaline air". Claude Louis Berthollet ascertained its
composition in 1785.
The Haber-Bosch process to produce ammonia from the nitrogen in the
air was developed by Fritz Haber and Carl Bosch in 1909 and patented in
1910.
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Process
Ammonia is synthesized from nitrogen and hydrogen by the
following reaction:
N2 + 3H2 2NH3
Steam reforming of NG
A) Synthesis gas
production
Feedstock
pretreatment and gas
generation
Carbon monoxide
conversion
Gas purification
B) Compression
C) Synthesis
Hydro-desulfurization
Raw materials
Air, natural gas (or other
hydrocarbons) and steam.
Removal of sulfur from feedstock,
e.g. natural gas, involves these
chemical reactions:
Primary reformer
After the removal of sulfur compounds, the gas is mixed
with superheated steam and fed into a primary reformer.
To achieve the required stoichiometric hydrogen/nitrogen
ratio for ammonia synthesis, the reforming reaction is split
into two sections.
In the first section, the primary reformer, the reaction
proceeds to achieve a partial conversion only [in
conventional plants 65 % based on methane feed, leaving
around 14 mol % methane (dry basis) in the effluent gas].
In the secondary reformer the gas is mixed with a
controlled amount of air.
The steam/carbon ratio used in modern commercial
primary reformers for natural gas is between 2.8 and 3.5.
Primary reformer
The burners primary reformers can be classified as top-fired, sidefired, terraced-wall, or, less common, bottom-fired reformers
Primary reformer
Primary reformer
Primary reformer has been identified as bottle-neck in increasing
the capacity of existing natural-gas-based ammonia plants.
This can be addressed by
having pre-reforming, installed at the up-stream
Secondary reformer
Alternate technologies
Kellogg reforming exchanger System (KRES)
Shift conversion
Any remaining carbon monoxide in the gas
mixture is converted to carbon dioxide in the shift
section of the process:
CO + H2O CO2 + H2
H = 41 kJ mol1
The shift conversion happens in two stages:
HTS | High temperature shift (iron oxide/chromium
oxide based catalyst at about 400 oC) that lowers the
CO content from 12-15% to about 3%.
LTS | Low temperature shift (copper oxide/zinc oxide based catalyst at about 200-220 oC) which lowers the
CO content further to about 0.2-0.5%.
Purification
Purification
Physical solvent e.g. polyethylene glycol dimethyl ether,
polyethylene glycol methyl isopropyl ether, polypropylene
carbonate etc
Selexol Process (UOP)
Sepasolv MPE process (BASF)
Fluor Solvent Process
Purification
Methanation
Any remaining amounts of CO and CO2 must be removed before the NH3
synthesis stage as they would poison the catalyst. Methanation is the
simplest method to reduce the concentrations of the carbon oxides well
below 10 ppm and is widely used in steam reforming plants.
The reaction is carried out over a supported nickel catalyst at a pressure
of 25 35 bar and a temperature of 250 350 C.
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
H = 206 kJ mol1
H = 165 kJ mol1
Le Chatliers Principle
If a chemical system at equilibrium experiences a change
in concentration, temperature, volume, or partial
pressure, then the equilibrium shifts to counteract the
imposed change and a new equilibrium is established.
N2 + 3 H2 2 NH3 + 92kJ
Decreasing the temperature of a system in dynamic
equilibrium favours the exothermic reaction.
4 volumes 2 volumes
an increase in system pressure due to decreasing
volume causes the reaction to shift to the side with
the fewer moles of gas.
Compression
Centrifugal compressor for make-up and
recycle gas compression of an ammonia plant
Compression
Advantages over reciprocating compressors:
Lower investment (single machines even for very
large capacities)
Lower maintenance cost
Less frequent shutdowns for preventive
maintenance
High reliability (low failure rate)
Other compression duties in the plants are also performed by centrifugal
compressors.
Ammonia synthesis
Ammonia synthesis
Mittasch
Ammonia synthesis
Ammonia synthesis
Schematic flow diagrams of typical ammonia synthesis loops
A) Synthesis loop for pure and dry make-up gas; B) Product recovery after recycle compression; C) Product recovery before
recycle compression (four-nozzle compressor design); D) Two stages of product condensation
a) Ammonia converter with heat exchangers; b) Ammonia recovery by chilling and condensation; c) Ammonia recovery by
condensation at ambient temperature; d) Synthesis gas compressor; e) Recycle compressor
Ammonia synthesis
reaction
rate v in
m3 NH3 /
(m3 cat
alyst s)
a) Locus of
temperatures
resulting in
maximum
reaction rate
Ammonia converter
Commercial Ammonia Converters
Commercial converters can be classified into two main
groups:
Internally cooled with cooling tubes running through the
catalyst bed or with catalyst inside the tubes and the cooling
medium on the shell side. The cooling medium is mostly the
reactor feed gas, which can flow counter- or cocurrently to the
gas flow in the synthesis catalyst volume (tube-cooled
converters).
The catalyst volume is divided into several beds in which the
reaction proceeds adiabatically. Between the individual catalyst
beds heat is removed by injection of colder synthesis gas
(quench converters) or by indirect cooling with synthesis gas or
via boiler feed water heating or raising steam (indirectly cooled
multi bed converter).
Ammonia converter
Assignment
Historical evolution of ammonia converter
technology.
15 hand written pages
Deadline : 8 November 2013
Modern integrated single-train ammonia plant based on steam reforming of natural gas (Uhde process)
a) Sulfur removal; b) Primary reformer; c) Steam superheater; d) Secondary reformer; e) waste-heat boiler; f) Convection section; g) Forced draft fan; h) Induced
draft fan; i) Stack; k) HT and LT shift converters; l) Methanator; m) CO2 removal solvent boiler; n) Process condensate separator; o) CO2 absorber; p) Synthesis
gas compressor; q) Process air compressor; r) Ammonia converter; s) High-pressure ammonia separator; t) Ammonia and hydrogen recovery from purge and
flash gas
Ammonia production based on heavy fuel oil (Linde flow scheme with Texaco gasification)
a) Air separation unit; b) Soot extraction; c) CO2 absorption; d) Methanol/H2O distillation; e) Stripper; f) Hot regenerator; g) Refrigerant; h) Dryer; i) Liquid N2 scrubber; j)
Syngas compressor; k) NH3 reactor