Process Industries I
(ChEg3214)
2. Nitrogen Industries
Outline
Nitrogen Industries
Ammonia synthesis
Nitric acid
Ammonium nitrate
Ammonium sulphate
Ammonium phosphate
Sodium nitrate
Potassium nitrate
Ammonia
Uses of Ammonia
Cont.,
The greatest use of ammonia is in fertilizers.
Ammonia is used in the production of liquid fertilizer
solutions which consist of ammonia, ammonium nitrate,
urea and aqua ammonia.
It
is also used by the fertilizer industry to produce
ammonium and nitrate salts.
Ammonia and urea are used as a source of protein in
livestock feeds for ruminating animals such as cattle,
sheep and goats.
Cont.,
Ammonia can also be used as a pre-harvest cotton
defoliant, an anti-fungal agent on certain fruits and as
preservative for the storage of high moisture corn.
Dissociated ammonia is used in such metal treating
operations as nitriding, carbonitriding, bright
annealing, furnace brazing, sintering, sodium hydride
descaling, atomic hydrogen welding and other
applications where protective atmospheres are required
Cont.,
Ammonia is used in the manufacture of nitric acid
The petroleum industry utilizes ammonia in
neutralizing the acid constituents of crude oil and for
protection of equipment from corrosion.
Ammonia is a widely used refrigerant in industrial
refrigeration systems found in the food, beverage,
petro-chemical and cold storage industries.
The food and beverage industry uses ammonia as a
source of nitrogen needed for yeast and
microorganisms.
Ammonia synthesis
Ammonia is produced in a process known as the Haber process, in which
nitrogen and hydrogen react in the presence of an iron catalyst to form
ammonia.
The hydrogen is formed by reacting natural gas and steam at high
temperatures and the nitrogen is supplied from the air.
Other gases (such as water and carbon dioxide) are removed from the gas
stream and the nitrogen and hydrogen passed over an iron catalyst at high
temperature and pressure to form the ammonia. It is the main industrial
procedure to produce ammonia.
N2 + 3H2 → 2 NH3 (ΔH = −92.4 kJ·mol−1)
Cont.,
THE HABER PROCESS
The Haber process now produces 100 million tons of
nitrogen fertilizer per year, mostly in the form of
anhydrous ammonia, ammonium nitrate, and urea.
3-5% of world natural gas production is consumed in the
Haber process (1-2% of the world's annual energy supply).
That fertilizer is responsible for sustaining one-third of the
Earth's population, as well as various deleterious
environmental consequences.
Generation of hydrogen using electrolysis of water, using
renewable energy, is not currently competitive cost-wise
with hydrogen from fossil fuels, such as natural gas.
Cont.,
Production of Ammonia synthesis gas
Two main types of production for ammonia synthesis
gas currently in operation are:
1. Steam reforming of natural gas or other light
hydrocarbons (Natural Gas Liquids, Liquefied
Petroleum Gas, Naphtha)
2. Partial oxidation of heavy fuel oil or vacuum
residue
About 85% of world ammonia production is based
on steam reforming process.
Steam reforming
Ammonia manufacturing based on
hydrocarbon
steam reforming consists of the following
phases:
Desulphurization
Steam treatment (Primary reforming)
Secondary reforming (in the presence of nitrogen)
Catalytic conversion of CO by steam (shift
conversion)
CO2 removal
Methanation (CO & CO2 removal)
Ammonia synthesis
Desulfurization
The first step in the process is to remove sulfur compounds
from the feedstock because sulfur deactivates the catalysts
used in subsequent steps.
Sulfur removal requires catalytic hydrogenation to convert
sulfur compounds in the feedstocks to gaseous hydrogen
sulfide using a cobalt molybdenum catalyst:
H2 + RSH → RH + H2S (gas)
The gaseous hydrogen sulfide is then adsorbed and removed by
passing it through beds of zinc oxide where it is converted to
solid
zinc sulfide:
H2S + ZnO → ZnS + H2O
The gas from the desulphuriser is mixed with process steam,
usually coming from an extraction turbine.
The steam/gas mixture is then heated further to 500-600°C in
the
convection section before entering the primary reformer.
Primary reforming
Catalytic steam reforming (primary
reformer) of the sulfur-free feedstock is used
to form hydrogen plus carbon monoxide:
CH4 + H2O → CO + 3H2
The primary reformer consists of a large
number of high–nickel chromium alloy tubes
filled with nickel-containing reforming
catalyst.
The overall reaction is highly
endothermic and additional heat is
required to raise the temperature to 780-
830°C at the reformer outlet.
Cont.,
The fuel energy requirement in the
conventional reforming process is 40-50%
of the process feed gas energy.
The flue-gas leaving the convection section
at 100-200°C is one of the main sources of
emissions from the plant. These emissions
are mainly CO2, NOx, with small amounts of
SO2 and CO
The secondary reformer
Only 30-40% of the hydrocarbon feed is reformed
in the primary reformer because of the chemical
equilibriums at the actual operating conditions.
The temperature must be raised to increase the
conversion.
This is done in the secondary reformer by
internal
combustion of part of the gas with the
process air, which also provides the nitrogen
for the final synthesis gas.
In the conventional reforming process the degree
of
primary reforming is adjusted so that the air
supplied to the secondary reformer meets both
Cont.,
The secondary reformer is raising the temperature to
increase the conversion by internal combustion of part
of the gas with the process air, which also provides the
nitrogen for the final synthesis gas.
The process air is compressed to the reforming
pressure and heated further in the primary reformer
convection section to around 600°C.
The process gas is mixed with the air in a burner and
then passed over a nickel-containing secondary
reformer catalyst.
The reformer outlet temperature is around 1,000°C,
and up to 99% of the hydrocarbon feed (to the primary
reformer) is converted, giving a residual methane
content of 0.2-0.3% (dry gas base) in the process gas
leaving the secondary reformer.
Shift Conversion
In
the High Temperature Shift (HTS conversion, the
gas is passed through a bed of iron
oxide/chromium oxide catalyst at around 400°C,
where the CO content is reduced to about 3% (dry
gas base), limited by the shift equilibrium at the
actual operating temperature.
Thereis a tendency to use copper containing
catalyst for increased conversion.
Thegas from the HTS is cooled and passed
through the Low Temperature Shift (LTS) converter
Cont.,
This LTS converter is filled with a copper
oxide/zinc oxide-based catalyst and
operates at about 200-220°C.
The residual CO content in the converted
gas is about 0.2-0.4% (dry gas base).
A low residual CO content is important for
the efficiency of the process.
Modern catalysts, however, require
extremely pure gases because they are very
sensitive to poisoning.
Moreover, they are not stable at higher
Cont.,
For many practical purposes, the water– gas shift
reaction is carried out using two adiabatic fixed bed
reactors with cooling between the two reactors .
In the first reactor, the “high-temperature (HT) shift
reactor”, most of the carbon monoxide is
converted.
This reactor operates at high temperature and
contains a classical iron-oxide-based catalyst.
The second reactor, the “low-temperature (LT) shift
reactor”, contains a more active copper-based
catalyst and operates at lower temperature.
Here the carbon monoxide content of the gas is
further reduced
Cont.,
The amount of catalyst in the LT shift reactor is
much larger than the amount needed to achieve
the required carbon monoxide conversion;
o extra catalyst, about 70% of the total catalyst
volume, is included to compensate for the
unavoidable deactivation and thus enable
continuous plant operation for at least two or
three years.
o Initially, almost all of the reaction takes place in
the top part of the catalyst bed, but deactivation
causes the reaction zone to move gradually
downwards
CO2 removal
The process gas from the low temperature shift
converter contains mainly H 2, N2, CO2 and the
excess process steam.
The gas is cooled and most of the excess steam
is condensed before it enters the CO 2 removal
system.
This condensate normally contains 1,500-
2,000ppm of
ammonia 800-1,200ppm of methanol. Minor
amounts of amines, formic acid and acetic acid
could be present in the condensate.
All these components should be stripped from
the condensate and/or recycled again.
Cont.,
The CO2 is removed in a chemical or a
physical absorption process.
The solvents used in chemical absorption
processes are mainly aqueous amine
solutions (Mono Ethanolamine (MEA),
Activated Methyl DiEthanolamine
(aMDEA) or hot potassium carbonates
solutions.
It can also be treated by adsorption in
pressure swing adsorber (PSA) using
proprietary solid adsorption media.
Methanation
The small amounts of CO and CO2,
remaining in the synthesis gas, are
poisonous for the ammonia synthesis
catalyst and must be removed by
conversion to CH4 in the methanator:
The final step in producing the hydrogen is
to use catalytic methanation to remove any
small residual amounts of carbon monoxide
or carbon dioxide from the hydrogen:
CO + 3H2 → CH4 + H2O
CO2 + 4H2 → CH4 +2H2O
Cont.,
The reactions take place at around 300°C in
a reactor filled with a nickel containing
catalyst.
Methane is an inert gas in the synthesis
reaction, but the water must be removed
before entering the converter.
This is done firstly by cooling and
condensation downstream of the
methanator and finally by
condensation/absorption in the product
ammonia in the loop or in a make-up gas
drying unit.
Ammonia synthesis
The gas mixture is now cooled, compressed
and fed into the ammonia synthesis loop.
A mixture of ammonia and unreacted gases
which have already been around the loop are
mixed with the incoming gas stream and
cooled to 5°C.
The ammonia present is removed and the
unreacted gases heated to 400°C at a pressure
of 330 barg and passed over an iron catalyst.
Under these conditions 26% of the hydrogen
and nitrogen are converted to ammonia.
Cont.,
The outlet gas from the ammonia converter is cooled from
220°C to 30°C. This cooling process condenses more the half
the ammonia, which is then separated out. The remaining
gas is mixed with more cooled, compressed incoming gas.
The reaction occurring in the ammonia converter is:
N2 + 3H2 → 2NH3
The ammonia is rapidly decompressed to 24 barg. At this
pressure, impurities such as methane and hydrogen
become gases. The gas mixture above the liquid ammonia
(which also contains significant levels of ammonia) is
removed and sent to the ammonia recovery unit. This is an
absorber-stripper system using water as solvent.
The remaining gas (purge gas) is used as fuel for the heating
of the primary reformer. The pure ammonia remaining is
mixed with the pure ammonia from the initial condensation
above and is ready for use in urea production, for storage or
for direct sale.
Simplified flow diagram of ammonia
production
Ammonia Fertilizers
Ammonium nitrate fertilizer
NH3(aq) + HNO3(aq) NH4NO3(aq)
Ammonium sulfate fertilizer
2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
Ammonium phosphate fertilizer
3NH3(aq) + H3PO4(aq) (NH4)3PO4(aq)
Urea fertilizer
2NH3(aq) + CO2(g) (NH2)2CO(aq) + H2O(l)
NITRIC ACID
Nitric Acid production
The most important single use of ammonia
is in the production of nitric acid.
A mixture of one part ammonia to nine parts
air is passed over a platinum gauze catalyst
at 850 °C, whereupon the ammonia is
oxidized to nitric oxide.
4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g)
2 NO (g) + O2 (g) → 2 NO2 (g)
3 NO2 (g) + H2O(l) → 2 HNO3 (aq)+ NO(g)
Major unit operations in Nitric Acid
Production
The major unit operations Technology
involved in the nitric acid
process are the same for all types of plant these
are:
Air filtration and Gas cooling
compression Gas compression
Air/ammonia mixing
Energy recovery and
Air/ammonia oxidation
cooling (dual pressure
over catalytic gauzes
plants only)
Energy recovery by
steam generation and/or
Absorption with the
gas re-heating production of nitric acid
1.Primary air filtration
Feed air contains, beside nitrogen and oxygen,
some inert gases, carbon monoxide and some
dust and impurities. Dust and impurities
harmfully affect the platinum catalyst efficiency,
therefore air must be filtered through a series of
filters.
Air is sucked (by NOx turbo- compressor set in
case of atmospheric or by an air compressor in
case of mono or dual pressure processes)
through a filter (usually candle felt filter
elements in case of atmospheric or special
paper filter elements).
2.Air Preheating:
In this step filtered air is introduced through a series of
steel pipes, in which flanges are provided on its outer
surface to increase the heating surface area.
Steam, at 3 kgm/cm2, 140ºC is passed through the
pipes and air outside. The steam condensate is
collected by steam traps and recycled to the boilers.
3.Ammonia evaporation and filtration
Anhydrous liquid ammonia is evaporated, superheated
and its pressure is maintained according to the
process. The ammonia is filtered (usually across
ceramic candle filters).
4. Air/ammonia mixture filtration
The purpose of this unit operation is to
increase purification of (air/ammonia) mixture.
Cylindrical filters of large diameters are used,
each one contains a porous ceramic candle
hanged on a disc with openings.
These candles permit the mixture to pass
leaving the impurities on their surfaces. After a
certain level of impurities, the filters needed to
be opened and washed with water then dried
by hot air.
The generated wastewaters from washing the
filters generate a pollution problem.
5.Ammonia Oxidation (converters)
The ammonia/ air mixture is introduced to the converter.
The ammonia air ratio should be strictly maintained at 12
% in case of atmospheric process or 13 % in case of dual
pressure process.
Ammonia is reacted with air on platinum/ rhodium alloy
catalysts in the oxidation section of nitric acid plants.
Nitric oxide and water are formed in this process.
The yield of nitric oxide depend on pressure and
temperature:
[P < 1.7 bar, T = 810-850 oC] NO
yield( 97%)
[P = 1.7-6.5 bar, T =850-900 oC] NO yield
(96%)
[P> 6.5 bar, T 900-940 oC] NO yield
(95%)
Cont.,
NH3 is reacted with air on a catalyst in the oxidation
section. Nitric oxide and water are formed in this process
according to the main equation:
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g
The reaction is reversible and exothermic. The water formed
in the reactions is condensed in a cooler condenser and
transferred to the absorption column.
Optimal conditions are high T, low P and short residence
time (minimize side rxn)
Nitrous oxide, nitrogen and water are formed
simultaneously in accordance with the following equations:
4NH3 + 3 O2 N2 + 6 H2O
4NH3 + 4 O2 N2O + 6H2O
Cont.,
Side reactions conditions
Temperature is adjusted in a range 800º-900ºC to minimize side reaction.
If T is above 900 nitrogen oxide will decompose to N2 and H2O.
4 NH3 + 3 O2 2N2 + 6 H2O
When it is below 800º C nitrous oxide will be formed which does not
produce nitric acid when dissolved in water.
4NH3 + 4O2 2N2O + 6H2O
When the main reaction is slow reactions NH3 and NO react to form N2 and
H2O.
4 NH3 + NO N2 + 6 H2O
THE RELATION OF THE AMMONIA BURNER EFFICIENCY AND
TEMPERATURE AT 1 AND 4 BAR
Ammonia/air ratio.
From an engineering point of view, the
combustion of ammonia is one of the most
efficient catalytic industrial reactions (the
theoretical maximum conversion would be 98 %
in a one bar plant).
The ammonia-air reaction mixture should
contain 14.38 % ammonia according to the
equation stoichiometry. However, a lower
NH3/air ratio is used for a variety of reasons, the
most important thing that the conversion
efficiency decreases at a high NH3/air ratio
mixing, so many plants add 10 % ammonia.
Reaction temperature
A high reaction temperature enhances ammonia
combustion, but decreases the conversion efficiency
due to the increased generation of N2 and N2O.
The oxidation generally takes place at temperatures of
between 850 and 950 °C, resulting in NO yields above 96 %.
Temperatures above 950 °C are possible, but catalyst
losses, mainly due to vaporization, then increase. The
reaction mechanism tends to be more selective towards
nitrogen and N2O formation at lower catalyst temperature.
Nitrous oxide (N2O) is unstable at these temperatures (i.e.
850 – 950 °C) and partly reduces to N2 and O2. A long
residence time and a high temperature in the catalytic
reactor promote this reduction. The reaction temperature is
directly related to the ammonia/air ratio: a 1 % increase in
the proportion of ammonia, increases the temperature by
approximately 68 °C.
Catalyst
4NH3 + 5O2 4NO + 6H2O
The combustion of ammonia is one of the most
efficient catalytic reactions with possible conversions
up to 98 percent.
The catalyst is platinum and the reaction occurs at 900
o
C. The catalyst is a Pt-Rh fine-mesh gauze, where the
Rh provides strength.
The biggest issue with this method is the loss of
precious metal at the reactor temperatures.
Recovery gauze is typically used to absorb platinum
oxide vapor and form an alloy. This gauze can
periodically be removed and platinum recovered.
Oxidation of NO and absorption in H2O
Nitric oxide is oxidized to nitrogen dioxide as the
combustion gases are cooled, according to the
equation:
2 NO + O2 NO2
Todescribe the kinetics of NO oxidation, a third-
order rate equation is used.
Thisreaction is unusual because the reaction is
quicker at lower temperatures. The reaction rate
has a negative temperature coefficient.
As a result of this process, part of the NO is
oxidized to nitrogen dioxide and di nitrogen
tetroxide
2NO + O2 2NO2 + N2O4
Cont.,
• The reaction model is quite complicated
because of the number of components
reacting (NO, NO2, N2O3, N2O4, etc.)
• Water runs down the absorption tower and
a reaction occurs to produce nitric acid.
• 3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)
Block diagram of nitric acid production
AMMONIUM NITRATE PRODUCTION
production of ammonium nitrate in industry
although simple, chemistry is technologically
challenging:
The acid-base reaction of ammonia with
nitric acid gives a solution of ammonium
nitrate.
HNO3 (aq) + NH3 (g) → NH4NO3 (aq).
This reaction is violent and very
exothermic.
Cont.,
The production process comprises three main unit
operations:
1. Neutralization,
2. Evaporation,
3. Solidification
Prilling
Granulation
Neutralization
Liquid ammonia is pumped from the ammonia
storage tank where it is vaporized in the
Ammonia Vessel and then superheated to
remove any liquid droplets before being fed
into the Neutralizer.
In the Neutralizer ammonia and nitric acid are
reacted together to form AN solution.
NH3(g) + HNO3(aq) → NH4NO3(aq) + Heat
The exothermic reaction provides sufficient
energy to produce process steam.
Cont.,
Need to Control the;
PH
Temperature
Feed rate
In order to reduce,
erosion of material of construction
Vaporization of ammonia
Ammonia may form ammonium hydroxide By
combining with steam
Evaporation to Concentrate the A.N
The solution will be steam heated in the multi
effect running under vacuum evaporation section.
The solution will be concentrated up to 97.5-
99.5% depending on whether ammonium nitrate
will be granulated or prilled.
Mixing the Filling Material:
In order to reduce the nitrogen content of A.N from
35% to 33.5%, the proper filling material is added
(about 4% by weight of powdered limestone or
dolomite or even kaolin).
Prilling or Granulation
The hot concentrated melt is either granulated
(fluidize bed granulation, drum granulation … etc.) or
prilled.
Prilling is the formation of round solid porous
spheres by allowing molten droplets to fall through
air.
In the Head Tank an additive is added to the AN
solution to assist crystallization.
Liquid AN is passed through spray nozzles with
suitable sized holes through which the solution
flows.
The counter current flow of air up through the
prilling tower cools and solidifies the prills during
their fall.
Cont.,
Drying, Screening
The ammonium nitrate (prills or granules) is dried
(usually in drums) using hot air (steam heated),
then screened to separate the correct product size.
The oversize and undersize will be recycled either in
the mixing tank (in case of prilling) or to the
granulator.
Final Cooling
The hot proper size granules, are then cooled
(against cooled and humid free air) down to 40°C
and coated with an anti-caking (usually amines)
and then conveyed to the storage.
Block flow diagram for ammonium nitrate production process
Uses of Ammonium Nitrate
Ammonium nitrate finds major applications
in:
Explosives
Fertilizers
freezing mixtures (for obtaining low
temperatures)
as a slow-burning propellant for missiles (when
formulated with other materials, including
burning-rate catalysts)
as an ingredient in rust inhibitors (especially for
vapor-phase corrosion) and as a component of
insecticides.
Ammonium sulphate [(NH4)2S04]
Ammonium sulphate (A.S) is a nitrogenous
fertilizer with an additional source of soluble
sulphur which is a secondary plant nutrient.
The majority of its production is coming from
coking of coal as a byproduct.
Ammonium sulphate is produced by the direct
reaction of concentrated sulphuric acid and
gaseous ammonia and proceeds according to
the following steps.
2NH3(g) + H2SO4(aq) [NH4]2[SO4]
ammonium sulfate
Cont.,
It is a white salt completely soluble in
water containing 20.6% of nitrogen and
24.0% of sulphur.
Ammonium sulfate is most widely available
as a dry granular fertilizer. The fertilizer is
100% water soluble.
Ammonium sulfate is widely used as a
sulfur source by blending with other
fertilizers such as urea.
PRODUCTION OF AMMONIUM SULPHATE
Ammonium sulfate is made by treating ammonia, often
as a by-product from coke-ovens, with sulfuric acid:
2NH3 + H2SO4 → (NH4)2SO4
A mixture of ammonia gas and water vapor is
introduced into a reactor that contains a saturated
solution of ammonium sulfate and about 2 to 4% of
free sulfuric acid at 60 °C. Concentrated sulfuric acid is
added to keep the solution acidic, and to retain its
level of free acid. The heat of reaction keeps reactor
temperature at 60 °C. Dry, powdered ammonium
sulfate may be formed by spraying sulfuric acid into a
reaction chamber filled with ammonia gas. The heat of
reaction evaporates all water present in the system,
forming a powdery salt.
Cont.,
Ammonium sulfate also is manufactured
from gypsum (CaSO4·2H2O). Finely divided
gypsum is added to an ammonium
carbonate solution. Calcium carbonate
precipitates as a solid, leaving ammonium
sulfate in the solution.
(NH4)2CO3 + CaSO4 → (NH4)2SO4 + CaCO3
Ammonium sulfate occurs naturally as the
rare mineral mascagnite in volcanic
fumaroles and due to coal fires on some
dumps.
Cont.,
During the reaction between concentrated
sulphuric acid and gaseous ammonia there
are three steps to produce Ammonium
sulphate.
1) Reaction of Ammonia and Sulphuric Acid
2) Crystallization
3) Drying of the wet Ammonium Sulphate
Crystals
1. Reaction of Ammonia and Sulphuric Acid
Liquid ammonia is evaporated in an
evaporator using 16 bar steam and
preheated using low pressure steam.
The stiochiometric quantities of preheated
gaseous ammonia and concentrated
sulphuric acid (98.5% wt/wt) are
introduced to the evaporator – crystalliser
(operating under vacuum).
These quantities are maintained by a flow
recorder controller and properly mixed by a
circulating pump (from upper part of the
crystallizer to the evaporator).
2. Crystallization
The reaction takes place in the crystallizer
where the generated heat of reaction causes
evaporation of water making the solution
supersaturated.
The supersaturated solution settles down to
the bottom of crystallizer where it is pumped
to vacuum metallic filter where the
Ammonium Sulphate crystals are separated,
while the mother liquor is recycled to the
crystalliser.
3. Drying of the wet Ammonium Sulphate
Crystals
The wet ammonium sulphate crystals are
conveyed (by belt conveyors) to the rotary
dryer to be dried against hot air (steam
heated) and then conveyed to the storage
area where it naturally cooled and bagged.
Uses of Ammonium Sulphate
The primary use of ammonium sulfate is as a fertilizer
for alkaline soils.
In the soil the ammonium ion is released and forms a
small amount of acid, lowering the pH balance of the
soil, while contributing essential nitrogen for plant
growth.
The main disadvantage to the use of ammonium sulfate
is its low nitrogen content relative to ammonium
nitrate, which elevates transportation costs.
It is also used as an agricultural spray adjuvant for
water-soluble insecticides, herbicides, and fungicides.
There, it functions to bind iron and calcium cations that
are present in both well water and plant cells. It is
particularly effective as an adjuvant for 2,4-D (amine),
glyphosate, and glufosinate herbicides.
Cont.,
As precipitant
Ammonium sulfate precipitation is a common
method for protein purification by precipitation. As
the ionic strength of a solution increases, the
solubility of proteins in that solution decreases.
Ammonium sulfate is extremely soluble in water
due to its ionic nature, therefore it can "salt out"
proteins by precipitation
As a food additive, ammonium sulfate is
considered generally recognized as safe
(GRAS) by the U.S. Food and Drug
Administration, and in the European Union it is
designated by the E number E517. It is used
as an acidity regulator in flours and bread.
Reading assignment
Ammonium
Phosphates production
Sodium nitrate
Potassium nitrate
END OF CHAPTER TWO
Thank you!
