PROCESS DESCRIPTION

Manufacturing of Ammonia from Natural Gas

1. Overall Conversion

The theoretical process conversions, based on methane feedstock, are given in the following
approximate formulae:-

0.88CH4 + 1.26Air + 1.24H2O ---- 0.88CO2 + N2 + 3H2

N2 + 3H2 ---- 2NH3

The synthesis gas production and purification normally take place at 25-35bar pressure. The
ammonia synthesis pressure is usually in the range 100-250bar.

2. Desulphurisation of feedstocks

Most of the catalysts used in the process are sensitive to sulphur and sulphur compounds. The
feedstock normally contains up to 5mg S.Nm-3 as sulphur compounds. The feed-gas is preheated to
350-400C, usually in the primary reformer convection section, and then treated in a
desulphurisation vessel, where the sulphur compounds are hydrogenated to H2S, typically using a
cobalt molybdenum catalyst, and then adsorbed on palletised zinc oxide:-

R-SH + H2--- H2S + RH

H2S + ZnO---- ZnS + H2O

In this way, the sulphur is removed to less than 0.1ppm S in the gas feed. The zinc sulphide remains
in the adsorption bed. The hydrogen for the reaction is usually recycled from the synthesis section.

3. Primary Reforming

The gas from the desulphuriser is mixed with process steam, usually coming from an extraction
turbine, and the steam/gas mixture is then heated further to 500-600C in the convection section
before entering the primary reformer. In some new the preheated steam mixture is passed through
an adiabatic pre-reformer and reheated in the convection section, before entering the primary
reformer. Also, in some plants, part of the process steam is supplied by feed-gas saturation. The
amount of process steam is given by the process steam to carbon molar ratio , which should be
around 3.0 for the BAT reforming processes. The optimum ratio depends on several factors, such as
feedstock quality, purge gas recovery, primary reformer capacity, shift operation, and the plant
steam balance. In new plants the optimum S/C-ratio may be lower than 3.0.

The primary reformer consists of a large number of highnickel 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 780-830C at the reformer outlet.

CH4 + H2O CO + 3H2

 CO + H2O CO2 + H2

The heat for the primary reforming process is supplied by burning natural gas or other gaseous fuel,
in the burners of a radiant box containing the tubes.

The flue-gas leaving the radiant box has temperatures in excess of 900C, after supplying the
necessary high level heat to the reforming process. Thus only about 50-60% of the fuels heat value
is directly used in the process itself. The heat content (waste heat) of the flue-gas is used in the
reformer convection section, for various process and steam system duties. The fuel energy
requirement in the conventional reforming process is 40-50% of the process feedgas energy. The
flue-gas leaving the convection section at 100-200C is one of the main sources of emissions from
the plant. These emissions are mainly CO2, NOx, with small amounts of SO2 and CO.

4. Secondary Reforming

Only 30-40% of the hydrocarbon feed is reformed in the primary reformer because of the chemical
equilibria 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 the heat balance and the stoichiometric synthesis gas requirement.

The process air is compressed to the reforming pressure and heated further in the primary reformer
convection section to around 600C. 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 1,000C, 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. The process gas is cooled to 350-400C in a waste heat steam boiler or
boiler/superheater downstream from the secondary reformer.

5. Shift Conversion

The process gas from the secondary reformer contains 12-15% CO (dry gas base) and most of the CO
is converted in the shift section according to the reaction:-

CO + H2O CO2 + H2

In the High Temperature Shift (HTS) conversion, the gas is passed through a bed of iron chromium
oxide catalyst at around 400C, where the CO content is reduced to about3% (dry gas base), limited
by the shift equilibrium at the actual operating temperature. There is a tendency to use copper
containing catalyst for increased conversion. The gas from the High Temperature Shift is cooled and
passed through the Low Temperature Shift (LTS) converter. This LTS converter is filled with a copper
oxide/zinc oxide-based catalyst and operates at about 200-220C. 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.

6. Carbon Dioxide removal

The process gas from the low temperature shift converter contains mainly H2, N2, CO2 and the
excess process steam. The gas is cooled and most of the excess steam is condensed before it enters
the CO2 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 recycled in BAT
processes. The heat released during cooling/condensation is used for the regeneration of the CO2
scrubbing solution, driving an absorption refrigeration unit and boiler feedwater preheat

The amount of heat released depends on the process steam to carbon ratio. If all this low level heat
is used for CO2 removal or absorption refrigeration, high-level heat has to be used for the feedwater
system. An energy-efficient process should therefore have a CO2 removal system with a low heat
demand.

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 carbonate solutions. Physical solvents are glycol
dimethylethers (Selexol), propylene carbonate and others. The MEA process has a high regeneration
energy consumption and is not regarded as a BAT process.Carbon dioxide removal which is consider
as BAT include aMDEA standard 2-stage process, Benfield process and Selexol or similar physical
absorption processes.

The typical range of heat consumption in the modern chemical absorption process is 30-60MJ.kmol-
1 CO2. The physical absorption processes may be designed for zero heat consumption, but for
comparison with the chemical processes, the mechanical energy requirements have also to be
considered. Residual CO2 contents are usually in the range 100-1,000ppmv, dependent on the type
and design of the removal unit. Contents down to about 50ppmv are achievable.

7. 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:-

CO + 3H2 CH4 + H2O

CO2 + 4H2 CH4 + 2H2O

The reactions take place at around 300C 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 in the product ammonia in the loop or in a make-up gas drying unit.

8. Synthesis and Compression of Ammonia

Modern ammonia plants use centrifugal compressors for synthesis gas compression, usually driven
by steam turbines, with the steam being produced in the ammonia plant. The refrigeration
compressor, needed for condensation of product ammonia, is also usually driven by a steam turbine.
The synthesis of ammonia takes place on an iron catalyst at pressures usually in the range 100-
250bar and temperatures in the range 350-550C:-
N2 + 3H2 2NH3

Only 20-30% is reacted per pass in the converter due to the unfavourable equilibrium conditions.
The ammonia that is formed is separated from the recycle gas by cooling/condensation, and the
reacted gas is substituted by the fresh make-up synthesis gas, thus maintaining the loop pressure. In
addition, extensive heat exchange is required due to the exothermic reaction and the large
temperature range in the loop. A newly developed ammonia synthesis catalyst containing ruthenium
on a graphite support has a much higher activity per unit of volume and has the potential to increase
conversion and lower operating pressures.

Synthesis loop arrangements differ with respect to the points in the loop at which the make-up gas is
delivered and the ammonia and purge gas are taken out. The best arrangement is to add the make-
up gas after ammonia condensation and ahead of the converter. The loop purge should be taken out
after ammonia separation and before make-up gas addition. This configuration is dependent on the
make-up gas being treated in a drying step before entering the loop. A make-up gas containing
traces of water or carbon dioxide must be added before ammonia condensation, with negative
effects both to ammonia condensation and energy. Conventional reforming with methanation as the
final purification step produces a synthesis gas containing inerts (methane and argon) in quantities
that do not dissolve in the condensed ammonia. The major part of these inerts is removed by taking
out a purge stream from the loop. The size of this purge stream controls the level of inerts in the
loop to about 10-15%. The purge gas is scrubbed with water to remove ammonia before being used
as fuel or before being sent for hydrogen recovery.

Ammonia condensation is far from complete if cooling is with water or air and is usually not
satisfactory .Vaporising ammonia is used as a refrigerant in most ammonia plants, to achieve
sufficiently low ammonia concentrations in the gas recycled to the converter. The ammonia vapours
are liquefied after recompression in the refrigeration compressor.

9. Steam and Power System.

Steam reforming ammonia plants have high-level surplus heat available for steam production in the
reforming, shift conversion, and synthesis sections, and in the convection section of the primary
reformer. Most of this waste heat is used for high pressure steam production for use in turbines for
driving the main compressors and pumps and as process steam extracted from the turbine system. A
modern steam reforming ammonia plant can be made energetically self-sufficient if necessary, but
usually a small steam export and electricity import are preferred.

Production of Urea from Ammonia (Stamicarbon Process)

1. Ammonia and Carbon Dioxide Compression

The hydrogen present in the carbon dioxide mixture is reduced by catalytic combustion to a
concentration of less than 100 ppmv; the catalyst used consists of platinum on a carrier. Part of the
air is used for this catalytic combustion, the remainder is necessary for maintaining an oxidising
atmosphere in the synthesis and high pressure recovery equipment for protection against corrosion.
The dehydrogenised CO2 mix is cooled down to 120C and fed to the bottom of the high pressure
stripper. This dehydrogenisation has the advantage that the off-gases contain so little hydrogen that
they are well outside the explosion limits of hydrogen-air mixtures.

2. Synthesis and Recovery

The carbon dioxide gas mixture flows to the stripper a falling film type shell and tube heat
exchanger, where It flows counter-currently against the reaction mixture leaving the urea reactor.
Unreacted gas is stripped from the reaction mixture and some decomposition of carbamate to
ammonia and carbon dioxide takes place. Stripped solution then flows to the recirculation section
for further removal of NH3 and carbamate.

Stripper overhead vapours flow to the high pressure condenser where they mix with ammonia feed
and the carbamate forming reaction takes place. Heat liberated by the reaction is used to generate
steam with low pressure, and the pressure on the shell side is used to control the degree of
carbamate conversion.

3. Recirculation

In this section essentially all of the non-converted ammonia and carbon dioxide are recovered from
the urea/carbamate solution leaving the bottom part of the stripper. This solution is expanded to
300 kPa via a level control valve. As a result of this expansion, part of the carbamate left in the
solution decomposes; the required heat is supplied by the solution, resulting in a temperature
decrease. The gas-liquid mixture is sprayed onto a bed of pall rings .The urea-carbamate solution
circulates from the bottom part of to heater where its temperature is raised to 130-1350 C, as a
result of which more carbamate is decomposed. The urea produced from this stage is then kept at
the storage tank before being transferred for the granulation process.

4. Granulation of Urea

Urea solution at a concentration of about 96% and at a temperature of about 136C is fed to the
granulator. In order to improve the granulation characteristics of the solution and the handling
properties of the urea granules, formaldehyde is added to the urea solution. The formaldehyde is
added in the form of a liquid urea formaldehyde precondensate. This is a product which allows a
higher concentration of formaldehyde to be transported and stored as a liquid. In the granulator, BL
301, solution is sprayed at a pressure of about 300 kPag onto granules suspended in a fluidized bed.
The solution injectors located in the bed require low pressure atomization air supplied by the blower
and heated in the atomization air heater to above the urea crystallisation temperature. Ambient air
is used as a fluidizing gas, with no dehumidification being required. Atomization and fluidization air
are extracted from the top of the granulator, together with some entrained dust, washed in a wet
scrubber and discharged by fan through a stack. Urea dust entrained with air amounts for the whole
plant to 4.5% of plant production and is recovered as a 45% solution which is recycled to the urea
plant. The washing process uses condensate from the urea plant.

The granulated product on the vibrating extractor flows to the fluidized bed cooler, which uses
ambient air supplied by the fluidization fans as cooling medium. Air exhausted from the cooler
contains some dust which is washed in a low pressure-drop scrubber and vented through a separate
stack. In the event ambient air is particularly cold or damp the preheater may be used. Similarly if
ambient air is particularly warm a chiller can be used.

Urea granules cooled down to the required temperature are lifted by the bucket elevator to the
screening section where they are separated into three fractions. Undersize granules are recycled
directly to the granulator oversize granules are first crushed in a roll mill and then fed back to the
granulator to be used as a seed material to initiate granulation. The on-size fraction is sent to
storage.

Overall Carbon dioxide

Methanation
Conversion removal

Synthesis and
Desulphurisation Shift conversion
compression

Primary Secondary
reforming reforming

Figure 1 The simplified process flow of Ammonia manufacturing using NC Braun process

Ammonia and
Granulaton of
Carbon Dioxide
Urea
compression

Synthesis and
Recirculation
recovery
Figure 2 The process flow of Urea using Stamicarbon