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PROCESS DESCRIPTION
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AMMONIA PLANT PROCESS DESCRIPTION

PROCESS ENGINEERING
PREPARED BY REVIEWED BY REVIEWED BY APPROVED BY
Rizwan Qasim Shan Nisar Adnan Mahmood 1 Shahbaz Ali
Process Engineer sH (PE !(est) UM(RE West) I DMJISD)

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Pakarab Fertilizers Limited Khanerval Road Multan, Ph+92-61-9220022,Fax+92-61-9220021

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Contents
1. Introduction: ............................................................................................................................. 2
2. Feed Gas Desulfurization .......................................................................................................... 2
3. Primary Reforming .................................................................................................................... 3
4. Secondary Reforming ................................................................................................................ 4
5. Carbon Monoxide Shift Conversion .......................................................................................... 5
6. Carbon Dioxide Removal........................................................................................................... 5
7. Methanation ............................................................................................................................. 6
8. Synthesis Gas Compression ...................................................................................................... 6
9. Ammonia Conversion ................................................................................................................ 6
10. Ammonia Refrigeration............................................................................................................. 7
11. Purge Gas Recovery Unit .......................................................................................................... 7
12. Nast ........................................................................................................................................... 8
13. Steam System............................................................................................................................ 8
14. Identification of Run Away Reactions in Ammonia Plant ......................................................... 8
14.1. Secondary reformer catalyst run away .............................................................................. 8
14.2. Methanator catalyst run away ............................................................................................ 9
15. PFD AND P&lDs INDEX .............................................................................................................. 9
15.1. PFD .................................................................................................................................... 9
15.2. P&IDs ................................................................................................................................ 9
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1. Introduction:

The Pakarab ammonia plant in Multan, Pakistan was designed by Kellogg for a nameplate capacity of
910 MTPD ammonia and commissioned in November 1978. Since then the following major
modifications have been implemented:
• A Petrocarbon designed cryogenic purge gas recovery unit was installed and commissioned in
February 1986 to increase the production to 960 MTPD.
• A Topsoe S-200 basket was installed in the two ammonia reactors in December 1993 to increase
the production to 1,050 MTPD.
• The reformer tube harps were replaced in December 1993 using the same HK 40 tube material.
• The BFW heater 123-C, and the feed / effluent exchanger, 121-C, were replaced with thermal
designs suitable for 1,150 MTPD production.
• A new ammonia refrigeration desuperheater, 134-C, were installed in series with the existing
refrigerant condensers 127-CA/CB.

The ammonia plant uses the KBR technology. The main process steps are:
• Feed Gas Desulphurization
• Primary Reforming
• Secondary Reforming
• Carbon Monoxide shift conversion
• Carbon Dioxide removal
• Methanation
• Synthesis gas compress
• Ammonia Conversion
• Ammonia Refrigeration
• Purge Gas Recovery Unit
• Nast
• Steam System

2. Feed Gas Desulfurization

The feed gas arrives at the battery limit at a pressure 45, kg/cm2g. The gas contains about 10 ppm
of organic sulphur. Sulfur is a poison to the reforming catalysts and the shift reactor catalysts. Any
sulfur that comes in contact with the reforming catalysts will reduce the catalyst activity. The low
temperature shift catalyst is permanently poisoned by small traces of sulfur.

This organic sulphur is converted to hydrogen sulphide using a hydrogen rich gas from another part
of the process in hydrotreator (107-D). This hydrogen mixed gas is preheated in feed preheater (103-
B) up to 399oC. Organic sulphur and any olefins reacts with hydrogen in hydrogenator in the presence
of NiMO catalyst to form hydrogen sulphide, reaction is as below.

RSH + H2 → H2S + RH
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COS + 3H2 → CH3OH + H2S

Hydrogen sulphide produced is adsorbed in two reactors in series (101-D / 102-D) which are filled
with zinc oxide. The gas should leave this section containing less than 0.25 ppm of sulphur. Following
is reaction across zinc oxide catalyst.

ZnO + H2S ↔ ZnS + H2O

3. Primary Reforming

Reforming is a process of converting hydrocarbons to hydrogen. This is carried out in radiant section
of the primary reformer (101-B). The desulphurized gas is mixed with steam and after preheats in
the mixed feed coil in the convection section of the primary reformer; the mixture is then distributed
to the catalyst tubes suspended in the radiant section of primary reformer. The vertical tubes are
packed with a metallic nickel catalyst and the reforming reaction temperature is approximately 820
C.

There are 378 vertical tubes in this furnace which are heated by ten rows of twenty each arch
burners firing downward from the top. Reformed gas from each bank of catalyst tubes pass upward
through a riser, out from the radiant section of the reformer, to water cooled external manifold
along which it is transferred to secondary reformer. The primary reformer exit is designed to leave
9%-10% of unconverted methane.

Following are the reactions detail in primary reformer tubes.

The main reforming reaction converts methane to hydrogen and carbon monoxide

CH4 + H2O ↔ CO + 3 H2 (Endothermic)

The water gas shift reaction converts carbon monoxide to carbon dioxide and more hydrogen.

CO + H2O ↔ CO2 + H2 (Exothermic)

The flue gases leave the floor of the radiant section of the furnace through brick tunnels and flow
to the convection section. This is an inverted U shape construction at the rear of the box furnace.
It is divided into two sections. Here various gases, steam and boiler feed water streams are heated
while flue gases are cooled down. Fourteen super heater burners are provided in the convection
section which assists in maintaining the super-heated steam temperature at desired level. The flue
gases of an auxiliary boiler also add in convection section. The total flue gases then pass through
an induced draught fan to the atmosphere.
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The primary reformer furnace attains maximum thermal efficiency by recovering heat from the flue
gases in the convection section. The hot flue gas leaving the radiant section of the primary reformer
are used in the convection section for the following service.

Hot Leg
 Mixed Feed Pre-Heat Coil
 Air-Steam Coil
 Hot Steam Super Heater

Cold Leg
 Cold Steam Super Heater
 Cold BFW
 Hot BFW
 Fuel Preheat

4. Secondary Reforming

The secondary reformer (103-D) is a refractory lined vessel packed with nickel catalyst. Here primary
reformer effluent containing 9%-10% methane joins steam and air mixture preheated in convection
zone of primary reformer. The mixture is burnt in the burner gun located at the inlet of secondary
reformer. This has double effect for raising temperature sufficiently high for further reforming
reaction to take place and to provide nitrogen required in the process later on.

In the upper section (combustion zone) of the secondary reformer, oxygen in the air reacts with
primary reformer effluent to according to the following exothermic reactions. The heat generated
during these reaction is used for further reforming reaction.

CH4 + O2 ↔ CO2 + 2H2 (Exothermic)

2H2 + O2 ↔ 2H2O (Exothermic)
CH4 + H2O ↔ CO + 3H2 (Endothermic)

The reforming reaction will reduce methane content to 0.3-0.4% at exit of secondary reformer. The
reforming reaction is highly endothermic and the gases leave the reactor at about 996 OC. The
extremely hot reformed gases now pass from the base of secondary reformer to a bayonet type
heat boiler. This is a vertical single pass exchanger with refractory lined on shell side. The water
(tube side) circulates due to thermosyphon effect from a steam drum located above the reformer
at a height of 36 meters. The shell of the reformer and primary waste heat boiler (101-C) are water
jacketed to reduce metal skin temperature. The gases are further cooled by a secondary waste heat
boiler (102-C) to 371OC before next stage of process. The air required in secondary reformer is
supplied by a two casing air compressor driven by a steam condensing turbine.
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5. Carbon Monoxide Shift Conversion

The reformed gases at this stage contain about 7.5 % carbon dioxide and 12.5% carbon mono
dioxide. Both of these oxides of carbon are poisonous for catalyst of ammonia converters. Carbon
mono dioxide is removed by shift reaction by means of residual steam which is present in the
reformed gases. This is known as the shift conversion. It is carried out in two stages, at high and
low temperature, over two different catalysts.
In the first reactor high temperature shift convertor (110-D), the carbon mono dioxide content is
reduced to 3.1% over a catalyst of reduced iron at 371oC. The reaction is exothermic and the outlet
gas temperature is about 431oC.

The gas is cooled by heat exchangers before entering the low temperature shift reactor (104-D)
which uses a copper catalyst. The gas enters the LT shift reactor at 242 oC and leaves at 255 oC.
Since this catalyst is very sensitive to sulphur compounds, it is protected by a guard bed of zinc
oxide in reactor top section. The carbon mono dioxide content is reduced here to about 0.5%.
Below is shift reaction.
CO + H2O ↔ CO2 + H2 (Exothermic)

6. Carbon Dioxide Removal

Process gas leaving L.T.S contains almost 17.5% of carbon dioxide. This is removed by absorption.
There are many processes for carbon dioxide removal and here catacarb system is being used. The
gas from exit of L.T.S is first cooled down, saturated with water and carbon dioxide is removed in
two absorption stages, by counter current contacting the gas with catacarb solution in a packed bed
absorber (101-E). The catacarb solution flows downward by gravity while the gas flows upward
through the tower. The raw synthesis gas, from the top of the absorber, its CO2 content now
reduced to 0.1% CO2, flows at 27.1 kg/cm2g to methanator.
The Catacarb solution consists of an aqueous solution containing the equivalent of 25% of potassium
carbonate which combines chemically with the carbon dioxide. Additives are present to enhance
the absorption rate, inhibit corrosion and to control foaming of the solution. The reaction which is
reversible by which carbon dioxide reacts with catacarb is as follows.

K2CO3 + CO2 + H2O ↔ 2KHCO3

The rich catacarb solution, from the bottom of the absorber is regenerated by flashing under low
pressure into a stripping tower (102-E) and by heating. The carbon dioxide is driven off and lean
catacarb solution from the bottom of the stripping tower is cooled and returned to top of absorber
for re-use. In addition to rich and lean solution, there is a semi lean catacarb solution, consisting of
partially regenerated catacarb solution is taken from a side stream draw off section of stripper tower
and delivered to the mid-section of the absorber tower.
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7. Methanation

The raw synthesis gas still contains a small percentage of carbon monoxide (0.6%) which was not
oxidized in shift reaction and a small percentage (0.1%) of carbon dioxide which was not removed
by catacarb system. Both these oxides are poison for the ammonia synthesis catalyst. These gases
are now removed by reaction with hydrogen to form methane and steam over a nickel catalyst.
The reactions are highly exothermic and is opposite of the reforming reaction. The reaction across
methanator is as below

CO2 + 4 H2 ↔ CH4 + 2 H2O

CO + 3 H2 ↔ CH4 + 1 H2O

The gas from exit of absorber is first preheated to 316 oC in Methanator feed preheater and it
leaves the reactor at about 364oC. Now the total oxides of carbon in the gas should be less than
10 ppm.
The gas is then cooled to 38oC and about 26 kg/cm2g is ready for next stage of process.

8. Synthesis Gas Compression

In order to bring the synthesis gas up to reaction pressure it is necessary to compress it up to 147
kg/cm2 g. This is carried out in a two case barrel type compressor. In the first case, the raw synthesis
gas is compressed from 26 kg/cm2 g to 70 kg/cm2 g. It is then cooled down to 8 oC and enters the
second casing where it is compressed to 154 kg/cm2 g. The makeup gas which is discharged from
1st stage of second case of the compressor is cooled down and then recombines with the recycle
gas from the system and is compressed up to 154 kg/cm2 g in the last wheel of the compressor.
The two case Clark compressors are driven by two AEG-Kanis turbines in tandem. The first turbine
is powered by HP steam at 105 kg/cm2g and exhausting at the MP (39.5 kg/cm
2 g) steam main pressure. The second turbine is powered by MP steam, is a condensing turbine. The
two turbines are connected by a coupling.

9. Ammonia Conversion

This is highly exothermic reaction which takes place over a reduced iron catalyst. There is normally
one reactor for this purpose but because of transportation limitations, it has been necessary to
supply two, which operates in parallel.
The reactors are vertical pressure vessels approximately 22 meters high and two meters dia
containing a basket with two beds of catalyst. The gas flows is from top and it goes down radially. A
cold shot is provided to control inlet temperature of 1st bed. Cold shots are provided to control the
inlet temperature of second bed. The incoming synthesis gas flows down between the two walls,
through the shell of the heat exchanger, then up through a central pipe to the top of the first bed.
Here it mixes with the quenches gas before entering the first bed. The gas from the exit of first bed
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enters the second bed after cool down in the inter bed heat exchanger as per desired temperature.
The gas from second bed flows out of the convertor after passing from the tubes of internal heat
exchanger.
The cooling of the reactor walls by the incoming gas helps to prevent hydrogen blistering of steel.
Passing through the convertors approximately 12% of the available nitrogen and hydrogen are
converted to ammonia at a reaction pressure of 151(135) kg/cm2. The synthesis reaction is shown
as below.

N2 + 3H2 ↔ 2NH3 + Heat

10. Ammonia Refrigeration

The cold condensed ammonia at 151 kg/cm2 and -23oC from the synthesis gas cycle is further cooled
in two stages by pressure drop through control valves down to -34oC and zero pressure.
The large amount of ammonia gas which is produced, in this auto cooling and from cooling of the
recycle gas in the synthesis loop is recompressed by a two casing ammonia compressor. This is
manufactured by GHH and is driven by an AEG-Kanis MP steam condensing turbine. In the first
casing ammonia gas is compressed up to 2.2 kg/cm2. In the second casing, there are two stages
arranged back to back to minimize axial thrust.
The compressed ammonia gas from the second casing at 16.8 kg/cm2 is condensed at 43 oC and the
liquid ammonia is further refrigerated by expansion in three stages. The gas from these stages flows
back to the compressor and the liquid ammonia at varying temperatures is used to cool down the
various parts of the synthesis gas loop.

The liquid ammonia produced is stored in a new double walled insulated storage tank contains 5000
M.tons of ammonia. The ammonia which boils off the tank is picked up by a separate package
refrigeration unit. A flare is also installed to cope with the excessive boiled off gases.
The ammonia can also be stored in the existing spherical tanks.

11. Purge Gas Recovery Unit

In 1986, Purge gas recovery unit was installed to separate hydrogen and fuel in the purges from the
recycle loop. The purges were burnt before as a fuel in primary reformer.
In this unit, the purges are taken from recycle loop of synthesis gas compressor. The purges are
consisting of ammonia, argon hydrogen and methane. Ammonia is separated by absorption
associated with stripping and returned back to refrigeration compressor suction drum 110-F. the
remaining gases, after removal of any moisture through absorbers, are cooled down to -190oC in a
cold box. Hydrogen and methane are separated here in cold box. Hydrogen is supplied to suction
drum of synthesis gas compressor and methane and argon are supplied to primary reformer as a
fuel.
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12. Nast

New Ammonia storage tank is a Double wall, full containment and have the capacity of 5000 MeT
as same of old Tank. Inner shell diameter is 26900mm and outer shell diameter is 28500mm.Inner
shell wall thickness varies from 13.3mm to 6.4mm from bottom to top respectively. Similarly outer
shell wall thickness varies from 10.7mm to 6.4 mm from bottom to top. The gap space between
inner & outer shell is 1600mm.Height of tank up to suspended deck is 15meters and height up to
dome roof is 20meters.Bottom of tank is also insulated & two layers of sand are present below
metallic bottom.
The system consists of two refrigeration units & a flare. Both refrigerating systems can be operated
in parallel as per their loading sequence & if pressure further increases then Flare can be use. Each
refrigerating system has capacity to liquefy 375 kg/hr of Ammonia vapors & flare has capacity of
burning 450 kg/hrs of Ammonia vapors.

13.Steam System

In the ammonia plant steam is generated at 105.5 kg/cm2g from waste heat boilers (101-C, 102-C
& 103-C) and auxiliary boiler. The bulk of the high pressure steam produced is used to drive the HP
turbine of 103-J, the synthesis gas compressor. This compressor turbine is in fact the main let down
station from high pressure to the medium pressure steam level. In addition a letdown station, which
consist of control valve and a desuperheater, and this is used to provide any extra let down required
and for use of the turbine should trip.
The medium pressure MP steam operates at 39.5 kg/cm2g and is used principally for driving
turbines and for supplying steam to the process.
An exhaust steam system operates at 3.3 kg/cm2g and is used principally for heating process
streams.

14. Identification of Run Away Reactions in Ammonia Plant

The hazards in handling dangerous substances mainly arise from the properties of these substances
and the processes involved. Unexpected reactions that may lead to uncontrolled developments
represent serious hazards for accidents. Below mentioned are identified run of reaction at Ammonia
Plant.

14.1. Secondary reformer catalyst run away

Partially reformed effluent from the primary reformer flows to the secondary reformer where
oxidation reaction takes place.

CH4 + O2 ↔ CO2 + 2H2 (Exothermic)

2H2 + O2 ↔ 2H2O (Exothermic)
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Heat of oxidation promotes rest of reforming required. Any increased flow of air to secondary
reformer can result in temperature Run away of catalyst bed.

14.2. Methanator catalyst run away

Methanator catalyst is design to convert CO and CO2. Rise in temperature depends on inlet CO and
CO2 concentration. As a rule of thumb, the Delta T is 60°C per 1 % CO2 and 74°C per 1 % CO
converted. For an ammonia Plant, the temperature rise would normally be 20-50°C and
CO2breakthrough from absorber could result in temperature Run away in methanator. High
temperature methanator trip security has been provided in case of temperature runaway.

15. PFD AND P&lDs INDEX

15.1. PFD

i. PR-01-PR32-001

15.2. P&IDs

i. 62-D1 GENERAL NOTES & LIST OF EQUIPMENTS

ii. 62-D2 FEED GAS HEATING
iii. 62-D3 SECONDARY DESULPHURISERS & RECYCLE HYDROGEN
iv. 62-D4 AIR COMPRESSOR & REFORMERS
v. 62-D5 SHIFT CONVERTER & METHANATOR
vi. 62-D6 CO2 ABSORBER
vii. 62-D7 SYNTHESIS GAS COMPRESSOR
viii. 62-D8 AMMONIA SYNTHESIS LOOP
ix. 62-D9 REFRIGERATION & AMMONIA PLANT
x. 62-D10 CO2 STRIPPER
xi. 62-D10-B CO2 CONDENSATE RECOVERY
xii. 62-D10-C RAW GAS SUPPLY TO BOC (POL)
xiii. 62-D11 CATACARB STORAGE FLUSHING DETAILS & CO2 BLOWER
xiv. 62-D12 PROCESS CONDENSATE STRIPPER WATER JACKETS
xv. 63-D1 FUEL GAS
xvi. 63-D2 RELIEF VALVE AND VENT SYSTEM
xvii. 63-D3 DIAGRAMATIC DETAILS
xviii. 63-D4 103J/JT LUBE AND SEAL OIL SYSTEM
xix. 63-D5 101-J/JT, 105-J/JT, 120-J/JT LUBE & SEAL OIL SYSTEM
xx. 63-D6 SEAL OIL SYSTEM
xxi. 63-D7 SEAL OIL SYSTEM
xxii. 63-D8 105-JAMMONIA REFRIGERATION COMP. GAS AND LUBE CONTROL
xxiii. 63-D9 101-J AND 101-JT LUBE CONTROL OIL
xxiv. 63-D10 INSTRUMENT AIR
xxv. 64-D1 DEAERATOR AND BFW PUMPS
xxvi. 64-D2 STEM GENERATION
xxvii. 64-D3 STEM DISTRIBUTION
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xxviii. 64-D4 STEM DISTRIBUTION

xxix. 64-D5 VACUUM EXHAUST AND CONDENSATE
xxx. 64-D6 COOLING WATER & DRINKING WATER SYSTEM
xxxi. 65-D1 NEW AMMONIA STORAGE TANK 1201-F
xxxii. 65-D1-A DELUGE VALVE FOR NAST (1201-F) COOLING WATER SYSTEM SCHEMATIC
DIAGRAM
xxxiii. 65-D2 TRANSFER PUMPS PIPING AND INTERVENTION DIAGRAM
xxxiv. 65-D3 REFRIGERATION UNITS 1201-L P&ID
xxxv. 65-D4 REFRIGERATION UNITS 1201-LS P&ID
xxxvi. 65-D5 FLARE 1201-V P&ID
xxxvii. 65-D6 PNEUMATIC, STEAM AND COOLING WATER FOR REFRIGERATION UNITS 1201-L /
1201-LS P&ID
xxxviii. 65-D7 NEW AMMONIA STORAGE TANK 1201-F GENERAL NOTES
xxxix. 2222-130 ABSORPTION SECTION HYDROGEN RECOVERY PLANT
xl. 2222-131 ABSORBER SECTION HYDROGEN RECOVERY PLANT
xli. 2222-132 COLD BOX SECTION HYDROGEN RECOVERY PLANT
xlii. 2222-133 AMMONIA RECOVERY SECTION HYDROGEN RECOVERY PLANT
 AMMONIA PLANT

Air Compressor
Atmospheric Air
101-J

Feed Pretreatment Reforming Section CO Shift Conversion

High
Natural Gas Low Temperature
Hydrotreater Desulphurizer Primary Reformer Secondary Reformer Temperature
Shift Converter
Feed 107-D 101-D & 102-D 101-B 103-D Shift Converter
104-D
110-D

CO2 Removal Section

Fuel for Burners

CO2 Absorber
101-E
Recovery Section Compression Section

NH3 to 110-F

Methanator
Synthesis Synthesis Gas

106-D
Purge Gas
Fuel to 101-B Converters Compressor
Recovery Unit
105-DA & DB 103-J
H2 to 104-F

Recycle

From 106-F Ammonia NAST

Refrigeration (Ammonia Storage)

110-J