Ammonia

Zuari Agro Chemicals Limited Ammonia plant is based on the ICI Steam
reforming process. Under this process, naphtha is used as feedstock. The
manufacturing process for Ammonia results in Carbon dioxide (CO2) being
produced as a by-product. Both the Ammonia and the Carbon dioxide generated
are essential for the manufacture of urea. Zuaris Ammonia plant has an installed
capacity of 660 metric tonnes per day. There are a number of processes that go
into the manufacture of Ammonia, including Hydro Desulphurisation (by IFP
Process), Reforming and Shift Conversion (by ICI Process), CO2 Removal (by
Benfield Process) and Synthesis (by TEC Process). The result of these processes
is liquid Ammonia that is either fed continuously to the Urea plant and NPK A and
NPK B plants or sent for storage. All process condensate that is generated from
the manufacturing process is fed to a hydrolyser / stripper. The Zuari plant was
the first one to adopt this high tech facility in India in 1977. Gas from the stripper
is scrubbed and utilised in the NPK A / NPK B plants, while the stripped
condensate water is recycled in a water treatment plantManufacturing
ProcessAMMONIA PLANTThe basic steps involved in the manufacture of
Ammonia are as given below :-The basic steps involved in the manufacture of
Ammonia are as given below :1.

Naphtha Desulphurisation

2.

Primary Reforming with Steam

3. Secondary Reforming in an auto thermal reactor using process air to fix

hydrogen to nitrogen ratio.
4.

2 stage shift conversion of carbon monoxide to carbon dioxide.

5.

CO2 removal using modified Benfield process.

6.

Methanation of residual carbon oxides

7.

Gas compression

8.

Ammonia Synthesis in two numbers parallel , radial S-200 converters.

9.

Ammonia Separation from converter gases using ammonia refrigeration

10. High pressure steam generation

11. Ammonia scrubbing of purge gas including Purge Gas Recovery Unit.
12. Process Condensate treatmentNaphtha DesulphurisationRaw Naphtha is
preheated / vapourised a fired process heater, mixed with H2 rich recycle gas
and then passed over CoMoX catalyst where sulphur is converted to H2S. The
H2S is separated from Raw Naphtha in a Stripper column from which the offgas is
routed to Auxiliary Boiler. Sweet Naphtha from the bottom of the H2S stripper
is cooled and sent to Sweet Naphtha storage.The Sweet Naphtha is subjected to
additional Desulphurising step. Sweet Naphtha is preheated / vapourised a fired
process heater, mixed with H2 rich recycle gas and then passed over CoMoX
catalyst where sulphur is converted to H2S. H2S is absorbed in the downstream
ZnO catalyst bed. ReformingDesulphurised Naphtha is mixed with process steam
and passed through reformer tubes containing nickel based catalyst. Since
reforming reaction is endothermic, heat is supplied through 84 nos. burner. The

temperature at the exit of the tubes is 780 deg.C. Most of the heat from the flue
gases is recovered in the convection section to preheat process steam, process
air, high pressure steam and combustion air. The partially reformed gas at 780
deg.C from primary reformer is mixed with process air in the secondary reformer
and flows through a bed of nickel based catalyst. Process air is supplied by a
centrifugal compressor given by a condensing turbine. The quantity of air is
controlled to provide nitrogen in the required proportion for the formation of
ammonia. The gas from the secondary reformer at 945 deg.C is routed through
two Waste Heat Boilers in series to generate high pressure steam at 100kg/cm2
(A). The cooled gas then flows to the high temperature shift converter.Shift
ConversionProcess gas enters HTS at about 350 deg.C. HTS is charged with Iron
oxide catalyst. At the exit of HTS the CO content is reduced to about 3.0% and
the temperature at the outlet of HTS is about 410 deg.C. This gas is then cooled
in process gas heat exchanger and in converted gas economizer to about 205
deg.C before admitting to LTS guard/LTS. In LTS converter CO is further reduced
to 0.25% by reaction over copper-zinc catalyst. The reaction is exothermic and
the temperature increases to 230 deg.C. The gas is cooled in process gas
reboiler where a large part of excess steam present in the gas condenses to
supply the regeneration heat for regenerating aMDEA solution. The process gas
is further cooled in a BFW exchanger to 88 deg.C before being admitted toCO2
absorber. Process Condensate formed in the two exchangers is separated in a
process gas knock out drum and sent for treatment in the condensate stripper.
CO2 RemovalCarbon dioxide is removed by absorption in Benfield solution in the
CO2 Absorber. CO2 rich Benfield solution is regenerated in the CO2 regenerator.
The heat for regeneration is supplied in the process gas reboiler by condensing
steam from the process gas and in solution exchanger by hot lean Benfield
solution exiting the CO2 generator. CO2 coming out of the regenerator is first
cooled in an indirect overhead condenser and subsequently in CO2 direct cooler
to 40 deg.C before supplying as a feed to the Urea Plant. MethanationProcess gas
from the CO2 absorber is preheated in the process gas exchanger to about 290
deg.C and sent to the Methanator. Methanator is charged with nickel based
catalyst. The residual CO & CO2 present in the gas are converted to methane by
reaction with hydrogen. The reaction is exothermic. The heat is used to preheat
boiler feed water going to the Reformed Gas Waste heat boiler. The process gas
is further cooled in gas final coolers using cooling water and subsequently in a
chiller using ammonia upto 10 deg.C before it flows to the synthesis gas
compressor. Ammonia Synthesis and RefrigerationThe synthesis gas which has
hydrogen to nitrogen volumetric ratio of 3:1 and a small percentage of inert
gases like methane and argon are compressed to the synthesis loop pressure in a
steam driven multistage centrifugal compressor. Dehydrator which is installed
in between the LP & HP casing of the synthesis gas compressor serves to purify
the synthesis gas. Here the final removal of all oxide impurities including water
takes place before the synthesis gas is introduced into the synthesis loop at the
suction of the recirculator, from where it goes into the converter alongwith the
recirculating gas. The operating pressure of the synthesis loop is about 115
kg/cm2(A). In the converters ammonia synthesis takes place over iron catalyst
at temperatures ranging from 400~500 deg. C. The ammonia concentration at
the exit of this converter is about 12%. Converter effluent gas is progressively
cooled in Synthesis Economiser, Synloop Boiler, Synthesis hot exchanger, BFW
heater before being admitted to the refrigeration section involving cold
exchangers and ammonia supercoolers. The gas is thus cooled to minus 20

deg.C and ammonia is separated. Unconverted gases are recycled back to

synthesis Convertors. Liquid ammonia is separated in a separator is taken to a
product letdown tank where the pressure is let down to 20kg/cm2(A). The gases
dissolved in liquid ammonia are released into letdown tank and are routed to
ammonia absorber where ammonia is removed. Gases free of ammonia are sent
as fuel to the auxiliary boiler. Product ammonia at minus 20 deg. C is heated to
5 deg.C and the chill is recovered in the refrigeration. Product ammonia at 5
deg.C is sent to urea plant/hortonsphere storage.Purge Gas Recovery UnitTo
control the inert composition in the loop a small stream of purge gas is taken out
and inerts, mainly methane and argon are separated in cryogenic purge recovery
unit. Purified hydrogen steam from the PGRU is sent back as make up gas to the
synthesis compressor. Process Condensate RecoveryProcess condensate from
knock out drum is sent to stripper unit where CO2, ammonia and methanol
impurities are stripped using live steam in a stripper column operating at
13kg/cm2 (A). The stripped gases are routed to the complex fertilizer plants for
recovery and the purified condensate is cooled and used as make up in the
cooling towers. High Pressure Steam GenerationThe high pressure steam
requirement (100 kg/cm2(A) ) and 490 deg.C is generated in the Reformed Gas
Waste Heat Boiler using the process heat at the outlet of secondary reformer.
The HP steam from the Waste Heat Boiler drums is superheated in the
convection section of the primary reformer. HP steam required over and above
generated in the RG Waste heat boiler is generated in the Auxiliary boiler using
Naphtha & Tail Gas as fuel.

NPK A
By adopting technology based on the slurry granulation process, the NPK A plant
can manufacture complex fertilisers (NPK) such as 28:28:0 (Uramphos), 18:46:0
(Samrat), 19:19:19 (Sampurna), and 14:35:14 (Sampatti). Zuaris NPK plant
incorporates the latest in pipe reactor technology, which ensures that the
fertilisers produced in this plant are some of the highest fertiliser grades in the
country. The NPK plant has reduced the effluent it generates by adopting
numerous processes. The particulate emissions of the NPK plant is considerably
lower than requisite industry standards owing to the utilisation of a high
efficiency scrubber. Water that is used for washing in the manufacturing process
is collected in a recovery tank, recycled, and used once again in the plant
reducing the effluent discharge.
Manufacturing Process
NPK granulation Plant consists of
1. Granulation
2. Drying
3. Size separation by sieving

4. Product cooling
5. Oversize crushing and conveying along with fines
6. Scrubbing of various air streams from granulator dryer and cooler
7. Dedusting.
Granulation
Recycle solids consisting of crushed oversize as well as the fines separated in the
process screens are routed back to the Ammoniator Granulator (AG) at the back
end through a chute. All the fresh solid feeds like Urea, Potash, filler are also
added to AG through the same chute. AG rotates at approx. 9 rpm causing a
rolling/cascading bed which mixes the incoming solids uniformly. Hot slurry
consisting of Ammonium Phosphates with a mole ratio of 1.4 is prayed on the
rolling/cascading bed through slurry spray nozzles. Liquid ammonia is introduced
below the rolling bed for further ammoniation and also supplies heat of reaction.
The rolling/cascading action of the solids on which the slurry is sprayed causes
the growth of granules through the process of agglomeration and accretion as
well as rounding off of the granules to spherical shape. The granules having
assorted size then flow to the dryer through a chute.
Drying
Solids flowing into the dryer has a moisture content of 1.8~2.2%. The co-current
dryer is a rotary equipment having specially designed flights to effect a good
cascading of the solids across the maximum cross section so that the air is
intimately contacted with the cascading solids and the solids are thus dried.
Depending on the operating temperature at the exit of AG, the firing in the
furnace generating hot air will vary. In the limiting case there will be no fuel
combusted in the furnace and the internal heat of the solids will be adequate to
dry the solids to a moisture content of 1.0 ~1.5% at the exit of dryer. Depending
on the grade produced (e.g. 19:19:19), air needs to be dehumidified before being
used in the dryer.
Sieving
Dried solids having a moisture content of 1.0 ~ 1.5% moisture are then routed to
3 nos process screens and distributed on the entire width of the screen through a
Screen Drag Feeder. The screens are double deck, vibrating type screens. The
upper deck mesh has 4mm opening and separates the oversize. The lower deck
mesh has an opening of 2mm and separates the undersize. The product is taken
out from the top of the bottom deck mesh from where it flows to the product
cooler through a conveyer belt.
Product Cooling
Product is cooled in a rotary drum cooler using air in a counter-current flow and
thereby the temperature of the product is reduced to 45 deg.C before sending
the product to the storage bins or for bagging.
Cyclones and Scrubbing
For effectively taking care of the dust and unreacted ammonia leaving with the
air stream in different operations in the plant, high efficiency cyclones and
venturi scrubbers as well as spray scrubber are employed. Dust and/or ammonia
ingress is generated in the equipment like the Preneutraliser , Ammoniator
Granulator, Dryer, Product Cooler, Crushing mills, screens, conveyers etc.

Cyclones separate most of the particulates from the air stream which are
recycled back. To take care of ammonia and smaller particulate emissions
following systems are installed.
Fumes Scrubbing System
The fumes scrubber scrubs the moist fumes coming out of Ammoniator
Granulator as well as the Pre-neutraliser. In the venturi scrubber, a two stage
scrubbing is employed using two venturis in series. Some Phosphoric acid is
added to the scrubber. The acidic media will effectively recover ammonia. Spray
nozzles are provided in the cyclonic separator of the venturi as a tertiary
scrubbing step.
Dryer scrubbing System
Dryer Scrubber scrubs the air coming out from the Dryer Cyclones. Originally the
plant had tumbler type of scrubber to scrub the fine particulate matter coming
from the dryer cyclones. As a part of on-going improvement in controlling
emissions, these tumbler type scrubbers have been replaced with venturi type
scrubbers which afford a much more intimate contact between the scrubber
liquor and the dust bearing gas. As a result, the efficiency of the venturi
scrubber is improved substantially.
Dedusting Scrubber System
Dedusting scrubber caters to scrubbing the dust laden gases from the Dedusting
system as well as the product cooler. This system incorporates a venturi type
scrubber to remove particulates from the incoming gases so that the gas exiting
the stack is well within statutory norms.
Liquid Effluent Control
Complex fertilizer plants like our NPK Plant A and NPK Plant B are net
consumers of waste water. This is because the principal reaction involved in the
production of complex fertilizers is the neutralisation reaction between Phos. Acid
and ammonia. This reaction is a highly exothermic reaction and is carried out in
the pre-neutraliser vessel. During the reaction a lot of heat is evolved and the
temperature of the process shoots up. A lot of water is required to be added in
the pre-neutraliser to control its temperature at approximately 125 deg.C. This is
done by consuming the scrubber liquor from the various scrubbing systems in
the plant. Scrubbing system typically contains approximately 30% solids formed
by reaction between Phos acid and ammonia recovered from the Granulator/preneutraliser/dryer air stream as well as the fertilizer dust recovered in the
scrubbers. Balance 70% is water. Thus, depending on the P205content of the
grade, phos. acid consumption varies and thereby the process water
consumption also varies. However, all the grades are net consumers of waste
(process) water.
Solid Waste Control
There is no generation of solid waste in the complex fertilizer plants like our NPK
A which uses imported concentrated phos. acid (P205 = 54%).