The Process Technology

of
Ammonia Industries
Introduction
 Ammonia is produced basically from
Hydrocarbon, water, air and energy.
 The hydrogen and energy source is usually
hydrocarbon.
 The other hydrogen and energy input required is
steam .
 The primary raw material or resources of
hydrogen and energy are hydrogen containing
materials such as Natural Gas (NG) or
petroleum or coal, water and biomass.

 Air provides Nitrogen and Oxygen

Chemical production Rank Catalytic Process

Sulfuric acid (H2SO4) 1 SO2 to SO3 ; heterogeneous

Ethylene (CH2CH2) 2
Lime (CaO) 3
Ammonia (NH3) 4 N2 + H2 ; heterogeneous
Sodium hydroxide (NaOH) 5
Chlorine (Cl2) 6 Electrocatalysis; heterogeneous

Phosphoric acid (H3PO4) 7

Propylene (CH3CHCH2) 8
Sodium carbonate (Na2CO3) 9
1,2-Dichloroethane (ClCH2CH2Cl) 10 C2H4 + Cl2 ; homogeneous
Nitric acid (HNO3) 11 NH3 + O2 ; heterogeneous
Urea (CO(NH2)2) 12
Ammonium nitrate (NH4NO3) 13
Benzene (C6H6) 14 Petroleum refining; heterogeneous

Ethylbenzene (C6H5CH2CH3) 15 Alkylation of benzene; homogeneous

Carbon dioxide (CO2) 16

Vinyl chloride (CH2CHCl) 17 Chlorination of C2H4; heterogeneous

Styrene (C6H5CHCH2) 18 Dehydrogenation of ethylbenzene;

heterog.
Terephthalic acid (1,4-(COOH)C6H4) 19 Oxidation of p-xylene; homogeneous
World production of Ammonia
In 2003, the world production capacity was 109 million tones
ammonia. Most of the production capacity was located in the
following regions [ IFA, 2005]:
 • Asia (46 % of world capacity)

 • East Europe and central Asia (14 %)

 • North America (11 %)

 • West Europe (9 %), with this share falling from a level of 13

% in 1988
 • Middle East (7 %)

 • Latin America (6 %)

 • Central Europe (4 %)

 • Africa (1 %) Ethiopia (0%)

 Oceania (1 %).
 80 % of the ammonia is currently used as the nitrogen
fertilisers.
 20 % being used in several industrial applications,
such as the manufacture of plastics, fibres,
explosives, hydrazine, amines, amides, nitriles and
other organic nitrogen compounds which serve as
intermediates in dyes and pharmaceuticals
manufacturing.
 Among the important inorganic products
manufactured from ammonia are nitric acid, urea and
sodium cyanide.
 .Liquid ammonia is an important solvent and is also
used as a refrigerant.
 A modern ammonia plant has a typical capacity of
1000 – 2200 tones/day
Life = Food =Fertlizers+ ( N2,P2O5 &K2O)
 H2SO4 (NH4)2SO4 20%N
ammonium sulfate

HNO3 NH4NO3 33%N

ammonium nitrate
NH3 + CO2 (NH2)2CO 45%N
urea

H3PO4 NH4H2PO4 11-18%N

ammoniated phosphates
11-48-0
18-46-0

HNO3/rock phosphate nitric phosphates

Rawmaterials
1.Hydrogen containing
materials
2.Steam
3. air
Raw material selection
 -Natural Gas (NG) is the most efficient
route for the production of ammonia.
 75-85% of the cost of anhydrous
ammonia is Natural Gas
 Ammonia manufacture is 70-80% of the
production costs of fertilizer
-The other routes are the partial oxidation of heavy oils and
Coal.
- Compared toNG, ammonia production with heavy oil is 30-
40% more energy intensive and with coal route 70-80% more

-The following is an approximate comparison of the energy

consumption, the investment cost and production cost for the
three feed stocks
 Natural gas is therefore the most appropriate
source of feedstock on all the three accounts.
 Natural gas will dominate as feedstock for
ammonia production in the foreseeable future.
 Coal may become a competing feedstock if the
prices of natural gas and petroleum products go
very high due to depleting resources.
 For the present time and near future, the
steam/air reforming process based on natural
gas is considered to be the most dominating and
best available technique for production of
ammonia.
Ammonia Technology
 Ammonia production Technology is almost
Hydrogen production Technology

 Hydrogen production Technology:

-Steam reforming
-Partial oxidation
-Water Electrolysis
 Ammonia
Industries

unit operations
MAJOR UNIT OPERATIONS OF NATURAL GAS BASE
AMMONIA SYNTHESIS TECNOLOGY
1. Gas`Storage
2. DESULPHURISATION
3. PRIMARY REFORMER
4. SECONDARY REFORMER
5. WASTE HEAT BOILER (WHS)/Heat recovery
6. HT SHIFT &LT SHIFT
7. Condensation process
8. CO2 REMOVAL (WASH)
9. METHANATION
10. Gas drying
11. COMPRESSOR
12. AMMONIASYNTHESIS
13. 13.Ammonia & CO2 Storages
Block Diagram Of The Partial Oxidation Process
Block Diagram Of The Partial Oxidation Process
 1. Feedstock desulphurization
 Natural gas typically contains significant levels of sulphur and
sulphur compounds,5-30 mg S/Nm3feed gas.
 Sulphur must be removed as it can poison the reforming
catalysts in downstream
 Sulphur compounds need to be reduced to a concentration of less
than 2 mg S/Nm3feed gas.
 . To remove the sulphur, the natural gas is heated to a
temperature of 300oC to 400oC in the presence of hydrogen
(usually recycled from the synthesissection), thereby
hydrogenating the sulphur compounds to H2S, which is then
adsorbed onto pelletized oxide for later disposal:

R-SH + H2 ⇔ H2S + R-H, (R = alkyl group)

H2S + ZnO ⇔ ZnS + H2O
desulphurization
2.Primary/Steam Reforming
 Gas from the desulphuriser is compressed, mixed with excess steam and
the preheated mixture enters the primary reformer at a temperature in the
range of 400 – 600 °C.
 The heated desulphurized natural gas and the steam then reacted in
the presence of a nickel or nickel-chromium catalyst.
 The composition of the outlet stream depends primarily upon the
following equilibria:
CH4 + H2O ⇔ CO + 3H2 206 kJ/mol
CO +H2O ⇔ CO2 + H2
 The first reaction is highly endothermic, and heat is supplied mainly
by firing natural gas.
 50% to 60% of the total generated heat is used in the reaction; the
heat released as flue gas to produce steam for use .
Primary reforming ( cont’d)
The hydrocarbon conversion rate in the primary reformer in
the conventional steam reforming plant is about 60-70 %.

The primary reformer consists of a large number of catalyst

filled tubes.

The applied steam to carbon molar ratio (S/C ratio) is typically

around 3.0; although the actual optimum ratio depends on
several factors, such as the feedstock quality, purge gas
recovery, primary reformer capacity, shift operation, and the
plant steam balance. In new plants, theoptimum S/C ratio may
be lower than 3.0.
Upon leaving the primary reformer, the gas is a mixture of CO2, CO,
H2O, CH4 and H2 at a temperature of approximately 800oC to 900oC.
Figure 2.2: Primart reformer radiant section and a
secondary reformer 1.inlet manifold, 2. burners,
3.reformer tubes, 4. outlet manifold, 5. process air
inlet,6.catalyst bed, 7.gas outlet
[12, Uhde, 2004]
3. Secondary Reformation
 In the primary reformer, only 30-40% of the hydrocarbon feed is
reformed to Hydrogen
 The main objective of secondary reforming is to add the nitrogen
required for the synthesis and to complete the conversion of the
hydrocarbon feed.
 This is done in secondary reformer where process gas is mixed
with preheated compressed air and then passed over nickel
catalyst. The reformer outlet temperature is about 1000°C, and up
to 99 per cent of the hydrocarbon feed to primary reformer is
converted.
 The further combustion of the un-reacted methane hydrocarbons raises
the temperature to over 1000oC, allowing the remaining methane to be
converted to H2 and CO. The temperature must be increased to increase
the conversion, the result that the methane is converted down to a residual
content of around 0.2 – 0.3 %.
 .The outlet gas from the secondary reformer consists primarily of CO2, CO,H2,
and N2 and it is cooled immediately to 350oC and 450oC downstream of the
reformer
Mass and energy flows for production of H2 from natural gas
with capture of CO2 C O v en ted 2
w ith ex h a u st

A ir
B o iler &
W a ter S tea m
F u el G en era to r
3 0 m o les
C H 4 In p u t S tea m
1 0 0 m o les
@ 8 8 0 k J /m o le
M eth a n e S tea m R efo rm er 2 8 0 m o les H 2
F eed sto ck & S h ift R ea cto r @ 2 8 4 k J /m o le
7 0 m o les
C H 4 + 2 H 2O C O 2+ 4H 2

C a p tu red C O 2
Secondary Reformer
Waste Heat Boiler
 The outlet gas from the secondary reformer
consists primarily of CO2, CO,H2, and N2
and it is cooled immediately to 350oC and
450oC in Waste Heat Boiler installed after
secondaryreformer
4.Shift conversion
The process gas from the secondary reformer contains 12 – 15 % CO
(dry gas base). Most of this CO will be converted in the shift
section to CO2 and H2., according to the reaction:
CO + H2O CO2 + H2 (- 41 kJ/mol)
 This reaction is carried out in two steps with intermediate heat

removal, a) a high temperature shift (HTS) and b) a low

temperature shift (LTS).
 In the HTS, process gas mixes with high-pressure steam and
passes over a FeO/Cr catalyst at a temperature of about400oC.
The process gas is then cooled to around 200oC the HTS , where
remaining CO is shifted to CO2 over a CuO/ZnO catalyst.
 The process gas is then condensed to remove excess steam
(condensate) before removal of CO2.
 Shift conversion (cont’d)
 a high temperature (HTS) favours reaction velocity, while low
temperature (LTS) favours product formations, so for this two shift
conversion steps are applied in series.
 Initially, the process gas is passed through a bed of iron
oxide/chromium oxide catalyst at 350 – 380 °C and then over a
copper oxide/zinc oxide catalyst at approximately 200 – 220 °C. The
final residual CO content of the gas is 0.2 – 0.4 %.
 New developments can enable an isothermal shift one-step
conversion to take place, applying an internal cooling of the process
gas with cooling tubes running through the catalyst layers.
 The shift process reduces CO to ppm which prevents poisoning of
the catalysts during the ammonia synthesis step. CO2 is much
easier to remove than CO.
5.Condensation Process
 The gas exiting the low temperature shift reactor is cooled
and after most of the excess steam is condensed and
removed it passes into the CO2 removal system.
 This is needed to prevent dilution of the CO2 removal
solvent and to maintain the correct equilibrium balance.
Condensates normally containing 1500 – 2000 ppm of
ammonia and 800 – 1200 ppm of methanol can be recycled
to the process in various ways.
 The heat released during cooling and condensation can be
used for several purposes, e.g. to regenerate the CO2
scrubbing solution, to drive an absorption refrigeration unit,
or to preheat the boiler feed-water.
6. Carbon Dioxide Removal
 After shift conversion and condensate removal, the process gas
contains mostly H2, N2, CO2.
 The CO2 (formerly CO) is also detrimental to the synthesis
catalysts, so it too must be removed.
 CO2 removal is by both chemical and physical processes,where
the CO2 either reacts with or is adsorbed onto a circulating
chemical solvent solution.
 This CO2/solvent solution is then regenerated via a stripper,
from which the CO2 may be either vented to waste or collected
for use elsewhere.
 The solvents used in chemical absorption processes are mainly
aqueousamine solutions, e.g. mono ethanolamine (MEA)
activated methyl diethanolamine (aMDEA) or hot potassium
carbonate solutions. Other typicalchemical solvents are glycol
dimethylethers (Selexol), potassium carbonate and others. The
regeneration of the solvents (in the stripper) occurs by steam
stripping or by flash tanks
 CO2 removal (cont’d)
 This process step removes the CO2 from the reaction gas and
the quantity corresponds to nearly all the carbon introduced as
feed gas into the overall process.

 The residual CO2 content is usually in the range of 50 – 3000

ppmv. The CO2 is removed in a chemical or physical
absorption process.

 Another emerging process is pressure swing adsorption (PSA).

This process has the potential tocombine in one step both the
classical CO2 removal and the methanation (next process
step).This is valid for all cases where the CO2 purity is
unimportant. However, if pure CO2 is neededas a product, then
a classical solvent scrubbing of the low pressure off-gas of the
PSA can beused to recover CO2.
6. Methanation
 Any small amounts of CO and CO2 still remaining in the synthesis
gas are converted to inert methane by catalytic methanation (which
is the reverse of the reforming reactions/ hydrogenation).
 The small amounts of CO and CO2, remaining in the synthesis gas,
can poison the ammoniasynthesis catalyst and must be removed
usually by conversion to CH4 by hydrogenation in the methanator:

CO + 3H2 ⇔ CH4 + H2O H = -206 kJ/mol

CO2 + 4H2 ⇔ CH4 +2H2O H = -165 kJ/mol
 These reactions take place at a temperature of around 300 °C in a
reactor filled with a nickel based catalyst. The residual concentration
of these carbon oxides is usually less than 10 ppmv.
Drying
 Methane is not involved in the synthesis reaction, but the water
formed must be removed before entering the converter.
 This is achieved by cooling followed by condensation/adsorption in
the gas drying unit using silicagel and molecular sieve
7 Compression
 Modern ammonia plants use centrifugal compressors to pressurise
the synthesis gas to the required level (100 – 250 bar, 350 – 550
°C) for ammonia synthesis. Molecular sieves are sometimes used
after the first compressor stage to remove the last traces of H2O,
CO and CO2 rom the synthesis gas. These compressors are
usually driven by steam turbines, utilising steam produced from the
excess process heat. A small quantity of condensates is removed
from the synthesis gas during compression. These condensates still
contain ammonia. Lubricating oils from mechanical equipment,
which are typically removed in oil/water separators, can contaminate
them.
 7. Ammonia Synthesis
 Purified synthesis gases are cooled and compressed, then they are passed over an
iron
 catalyst in the ammonia converter. Synthesis typically occurs at 20 MPa to 30 MPa at
 a temperature of 350oC to 550oC, but it is reversible, such that the amount of
 ammonia formed depends strongly upon temperature and pressure in the reaction
 vessel – a matter of primary importance to the plant operator:
 N2 + 3H2 ⇔ 2NH3 (8)
 Even at optimum temperature and pressure, only 20-30% of the synthesis gas reacts
 per pass. Formed NH3 is removed by refrigeration, and unreacted gases are recycled
 back to the converter. In order to produce sufficiently low temperatures to favour
 ammonia condensation, pressurized ammonia is itself used as a refrigerant. Product


ammonia is sent to atmospheric storage tanks equipped with refrigeration .
 The synthesis of ammonia takes place on an iron catalyst at pressures
usually in the range of 100 – 250 bar and at temperatures of between 350
and 550 °C:
N2 + 3H2 d2NH3 gH0 = -46 kJ/mol
 Only 20 – 30 % of the synthesis gas is converted per pass to ammonia, due
to unfavourable equilibrium conditions. The unreacted gas is recycled after
removing the ammonia formed.Fresh synthesis gas is supplemented in the
loop.
 As the exothermic synthesis reaction proceeds, there is a reduction in
volume and so a higher pressure and lower temperature favours the
reaction. The temperature of the catalyst needs to be controlled, as the heat
of reaction at the necessary equilibrium and reaction rate produces a rise in
temperature. Subdividing the catalyst into several layers is one technique
which can achieve this temperature control. In this technique, between the
layers, the gases are cooled either directly by adding cooled synthesis gas
or indirectly by generating steam. Various converter designs can be utilised
for this purpose
 For ammonia condensation from the loop, cooling with just water or air is
insufficient to achieve low ammonia concentration at the inlet. For this reason,
vaporising ammonia is used to chill the gas. The ammonia vapours are liquefied
by means of a refrigeration compressor. The various synthesis configurations
may differ with respect to the point where the make-up gas is added or where
liquefied ammonia and purge gas is withdrawn. New developments refer to the
use of more active catalysts such as cobalt-promoted iron and ruthenium. These
catalysts allow a lower synthesis pressure and a lower energy consumption to be
achieved (see Section 2.4.17).
 Conventional reforming with methanation as the final purification step produces a
synthesis gas containing unreacted gases and inerts (methane and argon). In
order to prevent the accumulation of these inerts, a continuous purge gas stream
has to be applied. Purge gas basically contains ammonia, nitrogen, hydrogen,
inerts and unreacted gases. The size of this purge stream controls the level of
inerts in the loop, keeping these to approximately 10 – 15 %. The purge gas is
scrubbed with water to remove ammonia, before then being used as fuel or
before being sent for hydrogen recovery.
Ammonia Synthesis
During industrial production of
ammonia, the reaction never reaches
equilibrium as the gas mixture
leaving the reactor is cooled to
liquefy and remove the ammonia.
The remaining mixture of reactant
gases are recycled through the
reactor. The heat released by the
reaction is removed and used to heat
the incoming gas mixture.
Ammonia Synthesis

Fe/K catalyst

exothermic
 Exothermic in the
N2(g) + 3H2(g) 2NH3(g) forward direction
-92 kJ mol-1

1. Pressure. The amount of pressure exerted is proportional to the

number of molecules. 4 molecules in the reactants, 2 molecules in
the products. Increase the pressure and the reaction opposes it by
moving to reduce the pressure – towards the products.

2. Temperature. Increasing the temperature will always increase the

rates in both directions at equilibrium. This is an exothermic reaction.
increasing the temperature will be opposed by moving towards the
reactants in the endothermic direction. This needs to be a compromise
between increased rate and low yield.
3. Remove the products and the reaction will oppose the change by
making more products.
 Le Chatelier’s Principle states that whatever
is done to a reaction, the reaction will act to
oppose it.
Example: If a product in an reversible
reaction is removed,more product will be
produced to re-establish the equilibrium

It may be applied to pressure, temperature

and concentrations of reactants and products.
 Exothermic in the
N2(g) + 3H2(g) 2NH3(g) forward direction
-92 kJ mol-1

Pressure: 200 atm (maximum safe pressure)

Temperature: 450oC (compromise between rate and yield)
Catalyst: Iron (used to increase the rate)

Finally, the ammonia is removed in a

condenser/cooler condensing it into a
liquid. This removes the product and
the reaction acts to restore the
equilibrium by making more.

Unused gases are recycled.

Increasing the pressure causes the equilibrium position to
move to the right resulting in a higher yield of ammonia
since there are more gas molecules on the left hand side of
the equation (4 in total) than there are on the right hand side
of the equation (2). Increasing the pressure means the
system adjusts to reduce the effect of the change, that is, to
reduce the pressure by having fewer gas molecules.

Decreasing the temperature causes the equilibrium position

to move to the right resulting in a higher yield of ammonia
since the reaction is exothermic (releases heat). Reducing
the temperature means the system will adjust to minimise
the effect of the change, that is, it will produce more heat
since energy is a product of the reaction, and will therefore
produce more ammonia gas as well
However, the rate of the reaction at lower temperatures is
extremely slow, so a higher temperature must be used to
speed up the reaction which results in a lower yield of
ammonia.
Rate considerations:
A catalyst such as an iron catalyst is used to speed up
the reaction by lowering the activation energy so that the
N2 bonds and H2 bonds can be more readily broken.
Increased temperature means more reactant molecules
have sufficient energy to overcome the energy barrier to
reacting (activation energy) so the reaction is faster at
higher temperatures (but the yield of ammonia is lower
as discussed above).
A temperature range of 400-500oC is a compromise
designed to achieve an acceptable yield of ammonia
(10-20%) within an acceptable time period.
At 200oC and pressures above 750atm there
is an almost 100% conversion of reactants to
the ammonia product.
Since there are difficulties associated with
containing larger amounts of materials at this
high pressure, lower pressures of around
200 atm are used industrially.
By using a pressure of around 200atm and a
temperature of about 500oC, the yield of
ammonia is 10-20%, while costs and safety
concerns in the building and during operation
of the plant are minimized
Yield NH3 mole fraction =ƒ(Temperature )
Yield NH3 mole fraction =ƒ( Pressure )
9 Steam and energy system
 The high amount of surplus heat available from the flue-gas of the primary
reformer, secondary reformer, shift conversion and the ammonia synthesis
requires the design of an efficient overall steam system in which high
pressure steam, usually in excess of 100 bar, is generated.
 Generally, all the high pressure steam will be fed to steam turbines driving
the synthesis gas compressor. At an intermediate pressure level, a part of
the steam is extracted from this turbine to supply the process steam for the
reforming reaction and to drive other compressors, pumps and fans. The
rest of the steam in the main turbine is condensed. Modern ammonia plants
do not import energy to drive mechanical equipment, but in fact in most
cases energy is exported to other consumers either as steam or as
electricity. A way to improve the plant efficiency is to use a gas turbine to
drive the air compressor and to use the hot exhaust gases as preheated
 combustion air for the reformer. In this case, the energy loss encountered
by steam condensation in the usually employed steam turbine is avoided .
 The same approach is also applied for the refrigeration
compressor, which is needed for condensation of the
ammonia product, and for the compressor used for
pressurising process air in the secondary reforming step.
A special advantage of these machines is that they can
be driven directly by steam turbines, using steam
generated in the plant mainly from waste heatThis allows
an efficient integration into the energy system of the
whole plant. In addition, the high degree of reliability and
the lower investment and maintenance costs, compared
to reciprocating compressors, improve the plant
economics
 Conventional Scheme – 4,000 MTPD
 The ‘conventional’ scheme can be scaled further up compared to the
capacities being considered today. This is a simple scale-up where
optimised operating conditions for the reforming section and the ammonia
synthesis loop in particular are defined in order to keep the equipment size
at a minimum.
 Looking at the investment cost, the reformer cost goes up more or less
proportionally with the number of tubes, and since the reformer cost is a
significant part of the overall plant cost, fully effect of economy of scale is
not applicable in this scheme when the reformer becomes larger and larger.
 From an energy point of view there is, however, no doubt that this scheme
is very energy efficient and gives the lowest specific energy consumption
figures of all schemes considered for large-scale plants.
 Our investigations show that up to a capacity of approx. 4,000 MPD this is
the preferred scheme.
Partial oxidation Tecnology
 The partial oxidation process is used for the
gasification of heavy feed stocks such as
residualoils and coal. Figure 2.3 gives an
overview of the process steps. The process is
very flexible and can handle the full range of
hydrocarbon feedstock, from natural gas up to
the heaviest asphalt including waste materials
such as plastics..
1. Air separation plant
 The air separation plant produces the oxygen
required for the partial oxidation step. This
unit also supplies pure nitrogen for the
stoichiometric demand in the ammonia
synthesis reaction and for the liquid nitrogen
wash applied for the final purification of the
synthesis gas
2 Gasification of heavy hydrocarbons
 The gasifier consists of an empty pressure vessel lined with heat
resistant alumina bricks.
 Hydrocarbons, oxygen and steam are introduced through nozzles
and react non-catalytically to yield carbon monoxide and hydrogen
at elevated pressures up to 80 bar:
2CHn + O2 2CO + nH2
 Apart from CO and H2, the reaction gas (raw gas) contains
approximately 3 – 5 % CO2, approximately 0.2 % CH4 and 0.5 %
soot depending on the quality of the feedstock. The CO/H2 ratio
depends on the feedstock composition and the quantity of steam
added to atomise the feedstock and to moderate the reaction, which
raises the temperature in the gasifier up to 1400 °C.
 The hot raw gas containing soot is cooled either by water quench or
in a waste heat boiler. The carbon is subsequently removed by
water scrubbing in a packed tower.
 3. Soot removal
 Different methods can be applied for recovering and recycling the soot. In
one process, it is extracted with naphtha. After separation from the water,
the soot-naphtha suspension is mixed with the hydrocarbon feedstock and
the naphtha is topped off in a distillation column. The topped naphtha is
recycled to the extraction section. The resulting carbon/heavy hydrocarbon
mixture is recycled to the partial oxidation reaction. Another variant extracts
the soot with light
gas oil in the form of carbon pebbles. These are screened off and recycled
to the heavy hydrocarbon feed. The extracted water is returned to the soot
scrubbing section. Heavy metals such as nickel and vanadium (introduced
with the feedstock) are suspended as oxides and are partially also present
as salts in the soot water circuit. To prevent an accumulation of these
compounds in the water circuit, some of the extracted water has to be
drained. The drained
water is cleaned by flocculation, applying settlers and/or filters, and disposed of
after a biological treatment. A paste containing vanadium and nickel is
recovered and sold to the metallurgical industry.
 There are presently two gasifier types
commercially used for ammonia production,
the“entrained flow gasification” and the
“moving bed gasification”. The applied
pressures range from 30 to 80 bar.
 The entrained flow gasification corresponds basically to the
partial oxidation concept of heavy hydrocarbons and takes place in
an empty pressure vessel. The differences from the partial
oxidation route are mainly in the method of introduction of the feedstock
into the gasifier. Thecoal is fed to the gas generator either as dry dust
via lock hoppers and rotary feeders or introduced as concentrated
water/coal slurry by means of a reciprocating pump. Flow direction and
use of waste heat boilers or quench and their degree of process
integration may differ in the individual processes as well as the
provisions to collect and remove the slag at the bottom of the gasifier.
The separation of entrained coal dust from the raw gas, containing
some fly ash, is very similar to carbon removal in the gasification of
heavy hydrocarbons. Reaction temperatures are around 1500 °C. The
raw gas has a low methane content (0.4 %), a moderate CO2 content
and CO/H2 ratios larger than 1.
 In the moving bed process, coarse grained coal (4 to 30 mm)
enters at the top of the gasifier via a lock hopper and is evenly
distributed over the cross-section of the surface of the coal bed. The
coal moves very slowly downward, and the gas leaves at the top of
the gasifier at flowrates smaller than the minimum fluidising velocity.
Ash is removed at the bottom of the gasifier using a revolving grid
with slots through which the gasifying agents, oxygen and steam,
are introduced. The temperatures are lower than in the entrained
flow gasification: 1000 °C in the lower section of the bed and around
600 °C at the top where the gas leaves. Compared to the entrained
flow gasification, the raw gas contains a higher amount of CH4 and
CO2 and a lower CO/H2 ratio because of the higher amount of
steam, which causes the water gas reaction to proceed parallel to
the partial oxidation reaction:
C + ½ O2 f CO gHo = -100.6 kJ/mol
C + H2Of CO + H2 gHo = 175.4 kJ/mol
 The hot reaction gas (raw gas) is first
quenched with recycled gas condensates
from the subsequent waste heat boiler.
Because of the lower gasification
temperature (a feature which saves oxygen)
the raw gas contains a higher amount of
impurities, e.g. tars, phenols and some higher
hydrocarbons, which are normally recovered
from the gas condensates. Additional
adsorptive pre-cleaning is necessary before
the gas can be fed to subsequent process
steps such as sulphur removal.
5 Sulphur removal
 Sulphur originating from the feedstock (up to 7 %) is
present in the raw gas, mainly as H2S.
 Depending on the process configuration, the raw gas is
cooled further under waste heat recovery and scrubbed
with a solvent, usually chilled methanol at -30 °C,
whereby a CO2/H2S fraction is separated and fed to a
Claus plant. In this unit, H2S is converted to elemental
sulphur by combustion with air using alumina catalysts.
Claus plants need an abatement system to reduce SO2
emissions.
 In an alternative process, the raw gas is sent directly to
the subsequent shift conversion without prior sulphur
removal. In this case, H2S is removed after the shift
conversion together with the total CO2 formed there.
6 Shift conversion
 Depending on the gasification design, i.e. waste heat boiler or
quench, additional steam has to be supplied ahead of the shift
conversion by saturation and direct injection. The conversion takes
place step-wise over iron-chromium oxide shift catalysts with
intermediate heat removal.
 A residual CO content of between 2 and 3 % can be attained. Over
the past twenty years,sulphur resistant catalysts containing cobalt-
molybdenum have in part replaced iron-chromium oxide catalysts.
These catalysts are active at temperatures ranging from 230 to 500
°C and allow shift conversion without prior sulphur removal. In this
case, the sulphur is recovered simultaneously with the CO2 after the
shift conversion. For the performance of the cobalt molybdenum
catalyst, the presence of sulphur compounds in the gas is essential.
7. CO2 removal
 After cooling the exit gas from the shift
conversion, the process condensate is
separated. The gas is chilled and scrubbed with
chilled methanol, which absorbs CO2 and H2S.
Stripping regenerates the loaded methanol. In
the process version without sulphur removal
ahead of the shift conversion, two fractions are
received in the regeneration: one is pure CO2,
which may be used for urea or other purposes,
the other contains H2S/CO2 and is fed to a
Claus plant.
8 . Liquid nitrogen wash
 For the final purification, normally liquid nitrogen
at approximately -185 °C is used to remove
residual CO, CH4, and most of the argon. At the
same time, nitrogen is added to the synthesis
gas. To prevent blocking of the cryogenic unit,
the traces of CO2 and H2O are separated from
the inlet gas by molecular sieve adsorption. The
resulting synthesis gas is very pure and purging
 in the synthesis loop is minimised. The rejected
waste gas fraction serves as a fuel.
Compression, steam and energy system
 The degree of energy integration is lower than in the
conventional steam reforming process. Separate
auxiliary boilers are necessary to provide steam for
mechanical energy and power generation, because of
the absence of hot reformer flue-gases. The NOx
emitted in this process mainly originates from the flue-
gas of the auxiliary boiler and fired preheaters.
Centrifugal compressors are used to compress air,
oxygen needed in the gasifier, nitrogen used in the liquid
nitrogen wash, ammonia used in the refrigeration
system, and the make-up gas and recycle gas
 in the ammonia synthesis loop. Steam turbines and
occasionally electrical energy are used to drive these
compressors.
9. Ammonia synthesis
 The ammonia synthesis loop is identical to the synthesis for steam
reforming
Uses of Ammonia
Ammonia is used in the manufacture of nitric acid; certain alkalies
such as soda ash; dyes; pharmaceuticals such as sulfa drugs,
vitamins and cosmetics; synthetic textile fibers such as nylon, rayon
and acrylics; and for the manufacture of certain plastics such as
phenolics and polyurethanes.

The petroleum industry utilizes ammonia in neutralizing the acid

constituents of crude oil and for protection of equipment from
corrosion. Ammonia is used in the mining industry for extraction of
metals such as copper, nickel and molybdenum from their ores.

Ammonia is used in several areas of water and wastewater

treatment, such as pH control, in solution form to regenerate weak
anion exchange resins, in conjunction with chlorine to produce
potable water and as an oxygen scavenger in boiler water
treatment.
Ammonia is used in stack emission control systems to neutralize
sulfur oxides from combustion of sulfur-containing fuels, as a
method of NOx control in both catalytic and non-catalytic
applications and to enhance the efficiency of electrostatic
precipitators for particulate control.

Ammonia is used as the developing agent in photochemical

processes such as white printing, blue printing and in the diazo
duplication process.

Ammonia is a widely used refrigerant in industrial refrigeration

systems found in the food, beverage, petro-chemical and cold
storage industries.

Ammonia is used in the rubber industry for the stabilization of

natural and synthetic latex to prevent premature coagulation.
The pulp and paper industry uses ammonia for pulping wood and
as a casein dispersant in the coating of paper.

The food and beverage industry uses ammonia as a source of

nitrogen needed for yeast and microorganisms.

The decomposition of ammonia serves as a source of hydrogen for

some fuel cell and other applications.

Ammonia is used by the leather industry as a curing agent, as a

slime and mold preventative in tanning liquors and as a protective
agent for leathers and furs in storage.

Weak ammonia solutions are also widely used as commercial and

household cleaners and detergents.
Option 2 Catalyst Technology and Reaction Engineering