1.

INTRODUCTION

Ammonia plant is based on steam reforming of natural gas. Ammonia plant consist of the
following sections

Natural gas supply

Desulphurisation section

Reforming section

CO conversion section

CO2 removal section

Methanation

Process condensate stripping section

Ammonia synthesis section

Refrigeration section

Ammonia absorption section

Purge gas recovery unit

For simplified flow diagram refer schematic flow diagram

1.1

NATURAL GAS SUPPLY

Natural gas, which is used as feed stock and fuel for Ammonia Plant and Power and
Steam Generation Plant is supplied at Offsite Gas Metering Station by Gas Authority of
India Ltd. from gas wells located in Krishna-Godavari Basin through pipe line. Natural
Gas is supplied at a pressure of 44 Kg/Cm 2g. After metering in Offsites, natural gas for
process feed is directly received at Ammonia Plant battery limit at 40 Kg/Cm 2 g and 40
o
C. Fuel gas through separate header after pressure reduction is received at the battery
limit at 3 Kg/Cm2g. Fuel gas is used for burners of Feedstock Pre-heater F-203, Primary
Reformer F-201, Auxiliary Super heater F-202 & Startup Heater F-501 in Ammonia Plant.
Feed gas received at battery limit goes to the desulphurisation unit for sulphur removal,
if any and subsequently processed to produce synthesis gas for Ammonia production.

1.2

DESULPHURISATION UNIT

The natural gas feed stock supplied to NFCL contains no H2S, but it is anticipated that
future supplies may contain sulphur compounds which have to be removed in order not
to poison the reforming catalysts and the LT shift catalyst. Natural Gas from battery limit
is heated to 385 oC in the Feed stock pre-heater F-203, and is passed through the
Hydrogenator. A bed of Nickel-Molybdenum catalyst is provided to catalyse the
hydrogenation of organic sulphur compounds to hydrogen sulphide. There are two types
of organic sulphur compounds that may be present in the feed stock. One is called
'Normal Sulphur' containing H2S, COS, CS2 and Mercaptans and the other is called 'Less

Reactive Sulphur', containing Thiophenes, Thioethers etc. In case of normal sulphur

except Mercaptans Hydrogen recycle gas is not consumed where as for less reactive
sulphur, recycle hydrogen is consumed as per the following hydrogenation reactions:

RSH
+
(Mercaptans)

H2

RH + H2S

R1SR
+
(Thioethers)

2H2

RH + R1H + H2S

R1SSR
+
(Thiophenes)

3H2

RH + R1H + 2H2S

If sulphur is present, natural gas is mixed with recycle gas from synthesis gas
compressor first stage discharge with flow of recycle gas around 1306 NM3/hr, in order
to avoid Carbon deposition on the catalyst due to catalytic cracking of higher
hydrocarbons if any. After preheating to 385 oC, the gas mixture passes to Hydrogenator
Reactor R-201 and reacts to produce H 2S. The above reactions are exothermic but
insignificant (which depends on the type of Sulphur that determines the number of moles
of hydrogen taken up). H2S produced in R-201 and that already present in Natural Gas is
then removed in H2S Absorbers R-202 A/B, thereby the gas will be free of H 2S. Each
absorber contains one bed of ZnO catalyst to absorb the sulphur. The absorbers are
operating in series with the second vessel acting as guard. When the ZnO in the first
vessel is getting exhausted, a break through of H2S from the first vessel may be
observed. The operation will then continue with the second vessel in service, while the
first vessel is being reloaded with fresh catalyst. The sulphur content at the exit of R202B shall be less than 0.1 ppm on dry volume basis at all times which is tolerant to
reforming catalyst.

The sulphur removal reaction in ZnO bed takes place as follows:

ZnO

H2S

ZnS

H2O

ZnO

COS

ZnS

CO2

ZnO reaction with S depends on:

Type of sulphur compounds.

Temperature: Increase in temperature will generally increase the ability of ZnO to

remove sulphur.

Capacity: As ZnO reacts with sulphur it gets saturated with sulphur and looses its
activity. Normal life of ZnO catalyst depends on the H 2S and sulphur concentration
in the natural gas.

1.3

REFORMING SECTION (GENERAL)

Steam reforming is a vital part of the front end in plants producing Ammonia.
Developments in metallurgy have allowed steam reformers to be operated at higher and
higher levels of temperatures, pressures and heat flux. The reforming process and the
design of the reformer are based on the reaction between methane and higher
hydrocarbons present in the natural gas with steam thereby generating CO, CO2 and
Hydrogen. The Hydrogen produced by the Methane reforming reaction is used to produce
Ammonia by combining with Nitrogen in the ratio of 3:1 which is the stoichiometric ratio
of hydrogen and nitrogen to produce ammonia.
The most important reactions taking place in the reformer are

CH4

H2O

CO

3H2

CO

H2O

CO2

H2

These reactions are taking place in the presence of a nickel-based catalyst. The
operating parameters maintained close to the equilibrium, are 769 oC and 30.5 Kg/cm2 g
and the maximum tube skin temperature allowable is 880 oC. The methane concentration
at the exit of the reformer is 14.03 %. The efficient operation of the reformer at the
above conditions will give rise to a methane leakage at the exit of secondary reformer of
0.6%. The higher slippage of methane has been designed taking advantage of PGR unit
incorporated. In addition to the recovery of hydrogen from the purge gas, there is
energy saving due to the lower heat flux required in the reformer resulting in reduced
firing, there by increasing the life of catalyst and reformer tubes.
PRIMARY REFORMING
Raw synthesis gas is produced by reforming natural gas to an intermediate level in the
primary reformer F-201 using super heated HS steam in presence of a Nickel based
catalyst at 33 Kg/cm 2 g pressure. The hot desulphurised natural gas and recycle gas
mixture from R-202B outlet is combined with HS steam (37 Kg/Cm 2 g 370 oC) to give a
steam to carbon mole ratio of 3.3:1.0. A small quantity of condensate from P-353 A/B
containing small percentage of Methanol and Ammonia is also mixed with steam for
subsequent recovery of H2 and to avoid pollution. The combined steam-natural gasrecycle gas mixture (Mixed feed) is preheated to 520 oC in the process gas convection
coil E-201 located in the waste heat recovery section of the primary reformer F-201
utilising the heat from the hot flue gases, leaving the reformer radiant section.

Following preheat, the gases are distributed through hair pin tubes into vertical reformer
tubes filled with Nickel catalyst. The tubes are placed inside a Furnace, where sensible
heat and endothermic heat of reaction are absorbed in the tubes by radiation from a
number of wall burners to the tubes. The primary reforming of natural gas is done in a
Topsoe design side fired furnace, in comparison to the top fired furnace, where the
maximum heat input is concentrated in the top part of the furnace. In the top fired
furnace during startup conditions with low flow, little or no heat of reaction in the tubes,
the maximum temperatures may well be found at the level of flames. In such furnaces
higher than desirable temperatures may be present in the top part of the tubes even
when the outlet temperature is not higher than the level recommended.
In the upper part of the top fired reformer, where the methane concentration is high and
hydrogen concentration is low, the potential for carbon formation is present. Due to the
radial temperature and concentration gradient in the tube, the risk zone extends
somewhat down along the hot tube wall. If this zone reaches a temperature level where
the rate of the cracking reaction becomes sufficiently high, carbon formation will take
place resulting in a "hot band". Top fired furnaces are more prone to this kind of
problem. Using the side-fired furnaces eliminates the above disadvantages of using top
fired furnace. In case of side fired furnace, the reformer outlet temperature increases
gradually from the top towards bottom. The tube skin temperature along the length of
the tube can be better-controlled in side fired furnace. The potential for carbon formation
with the age of the catalyst, the possibility of higher tube skin temperature at the bottom
than from the top is better controlled using side fired furnace.
The primary reformer furnace consists of 190 tubes, inserted in two parallel chambers
called the radiant zone. Each chamber has got 95 tubes in a single row. Each row has
been divided into 5 sections. Each section has got 19 tubes. Reformer tube outlets from
both chambers are connected to hot collectors through pigtails, which are placed outside
the Primary Reformer radiant zone. Hot collectors are again connected with cold
collector. The furnace operates with side firing of fuel gas on both sides of each row of
tubes to develop a process gas temperature of about 769 oC at the catalyst tube outlet.
There are 360 side-fired burners arranged in 6 rows per wall. Each row is having 15
burners. The type of primary reformer burners is of LP Radol Burner, which is of rugged
construction. Natural gas pressure reduced to 3 Kg/Cm 2g at Offsite is used as fuel for the
LP Radol Burners. The flame shape should be flat against the heated Muffle Block
surrounding the air nozzle. The excess air shall be 10%. The Reformer is loaded with
20.05 M3 of R-67-7H Nickel based unreduced catalyst at bottom and 6.68 M 3 of R-67R-7H
Nickel based pre-reduced catalyst at top. Both are cylindrical having seven holes with OD
16 mm and height 11 mm. Inside the catalyst tubes the natural gas steam reforming
reaction takes place.

REFORMING REACTIONS

The following reactions take place simultaneously, producing a mixture of H 2, CO, CO2,
CH4 and excess H20 when hydrocarbons undergo steam reforming over Nickel catalyst:

CnHm +

2n H2O

n CO2 +

(2n+m/2) H2 Heat (1)

CH4

2 H2 O

CO2

4 H2 Heat

(2)

CH4

H2O

CO

3 H2 Heat

(3)

CO2

H2

CO

H20 Heat

(4)

Reactions start at 500 oC for the higher hydrocarbons and 600 oC for methane.
REFORMING VARIABLES
Reaction (3) requires small amount heat only, whereas the heat required for 1 and 2
dominate the picture.
TEMPERATURE
The effect of increasing reforming temperature on the effluent gas composition is to
reduce the methane and carbon dioxide content. On decreasing reforming temperature,
the effects are reversed. On decreasing temperature, there is a theoretical risk of carbon
formation according to the Bourdard reaction when the gas is cooled.

2 CO

CO2

C (Soot)

Under the chosen conditions, the above reaction can only take place below 750 oC
because of the equilibrium conditions and above 650 oC because the soot formation
reaction rate is too slow to have any practical importance below 650 oC.
STEAM/CARBON RATIO
The unit operation is most economical at conditions closely approaching the design
steam to carbon mole ratio of 3.3:1.0. However, increasing steam to carbon ratio will
shift the above equilibrium reactions to the right with a net effect of decreased methane
and carbon dioxide and increased carbon monoxide and hydrogen in the reformed gas.
PRESSURE
As the reforming reaction proceeds with an increase in the number of moles, a higher
pressure will drive the reaction in the undesired direction, resulting in a higher methane
content at the reformer exit, if other factors remain unchanged. In spite of the above
effect, economy of design has required reforming pressure to be increased in order to
save on synthesis gas compression costs. Also higher-pressure results in the additional
advantage of making the heat of condensation of gases exit the LT CO Converter

available at higher temperature thereby facilitating the recovery of this heat by BFW
preheating.
Hence, reforming pressure is fixed by an optimal balance between the reaction
equilibrium on one hand and compression power and heat recovery on the other. Equally
important is the pressure drop across the reformer tubes. An increase in pressure drop
indicates possible catalyst fouling or partial blockage of tubes due to some other reason.
CARBON FORMATION
In the operation of the primary reformer carbon may be formed partly outside the
catalyst, partly inside the catalyst. Carbon deposits outside the particle will increase the
pressure drop over the catalyst bed and deposits inside the particles will reduce their
activity and their mechanical strength. Thermodynamically carbon formation is not
possible under the conditions foreseen, if equilibrium is obtained for each step. If the
catalyst, however, is poisoned, e.g. by sulphur, it will loose its activity and carbon
formation is likely to occur. At very low steam to carbon ratio, there will be a possibility
of carbon formation, which would result in carbon deposits, especially inside the catalyst
particles. If the catalyst is insufficiently reduced, or if it is partly oxidised during
production upsets, without subsequent reduction, carbon formation may take place.
Carbon deposition will hinder reforming and reduce heat transfer so that the tube wall
temperature will rise in that zone producing 'hot bands' and subsequently 'hot tubes'.
Precautions should be taken to prevent carbon formation on reforming catalyst for
successful reformer operations.
FLUE GAS SYSTEM
The reformer furnace is designed to obtain maximum thermal efficiency by recovering
heat from the flue gases leaving the reformer radiant section. The hot flue gas from top
at 980 oC passes through downward and horizontal flue gas duct. The flue gas blower (K201) induces the desired draft of 375 MM WC. The flue gases enter the waste heat
recovery section and give up heat successively to the various coils. At the outlet, the flue
gas temperature is reduced to approx. 170 oC as any further reduction in temperature
may result in condensation of sulphur compounds if any present in the flue gas.
COMBUSTION AIR
Combustion air to the forced draught radiant burners of primary reformer and auxiliary
steam super heater is supplied by Combustion Air Blower, K-202 after preheating to 293
o
C in combustion air pre-heater E-204 by recovering sensible heat of the flue gases.
SECONDARY REFORMING
The partially reformed gas exit Primary Reformer contains 14.03 mole % of CH 4 (dry
basis). The methane content is further reduced to 0.6 mole percent (dry basis) at high
temperature in the secondary reforming step. In the Secondary Reformer, R-203, the
heat is supplied by combustion of part of the gas achieved by mixing air into the gas as

compared to the indirect heat by firing in the Primary Reformer. This combustion
provides heat for the rest of the reforming in R-203. The methane slip exit Primary
reformer is so adjusted that the process air supplying the reaction heat in the Secondary
Reformer will give the Hydrogen/ nitrogen ratio of 3:1 in the syn. gas. It is desirable to
reduce the methane content of the process gas to a low level in order to keep the level
of inert gases low. The methane content exit R-203 is dependent upon the methane slip
at the Primary Reformer outlet at specified conditions. The high CH 4 slip at F-201 outlet
gives rise to CH4 slip of 0.6 mole %(dry) at R-203 outlet at 943 oC. Since air quantity is
fixed when PGR Unit is running, the H2:N2 ratio in the make up gas is 2.78 which gives
rise to 3:1 at Ammonia Synthesis Converter inlet by recovering H 2 from PGR. The inert
concentration is maintained at 8% in Synthesis loop at Converter inlet.
The partially reformed gas from primary reformer is directed to the refractory lined
Secondary Reformer R-203 at 31 Kg/Cm 2g and 769 oC. Process air supplied by Process
Air Compressor K-421 at 33 Kg/Cm 2 g and 177 oC is preheated to 550 oC in E-202A/B
coils located in convection section of F-201, passes vertically downward through the
centrally located Air Mixer to the Secondary Reformer R-203. Instantaneous mixing and
rapid combustion of part of the partially reformed gas takes place with air in the upper
empty space of R-203, resulting in a sharp rise of temperature to about 1200 oC. This
combustion provides heat for the rest of the reforming. From the empty space, the gas
passes down the Nickel catalyst bed where the reforming reaction is completed with
simultaneous cooling of the gas. The outlet temperature will be about 943 oC and the
methane concentration will be approx. 0.6 mole percent. In the combustion zone of
Secondary Reformer, the following reaction takes place between process gas and air and
O2 gets completely consumed.

2H2

02

2H20

Heat

CH4

202

CO2

2H20

(1)
+

Heat

(2)

Reaction (1) is predominant.

In the catalyst bed methane reforming reaction takes place as follows:
CH4

2 H2 O

CO2

H2

CO2

4H2

Heat

CO
(Shift Conversion)

H20

Heat

The catalyst in the secondary reformer comprises of a layer of alumina balls and alumina
guard tiles at the top and 30 M3 Nickel based catalyst in the middle. A layer of electro
fused alumina lumps are also provided at the bottom over the refractory dome as
catalyst support.
HEAT RECOVERY FROM REFORMED GAS

Reformed gas with unreacted process steam at 943 oC from the bottom of Secondary
Reformer R-203 passes through the tube side of special type of Waste Heat Boiler E-208.
This Waste Heat Boiler consists of two compartments, which is castable refractory lined.
The total gas is passed through tube side of the first compartment where as the second
compartment has been provided with internal bypass to control exit temperature. A
temperature controller regulates flow through the bypass to maintain HT Shift Converter
inlet temperature at about 360 oC. Sensible heat of the process gas exit R-203 is utilised
to generate KS steam in waste heat boiler. Boiler feed water from steam drum is fed to
the shell side of E-208 through number of down comers and steam/water produced are
sent back to the steam drum through number of risers by thermo syphoning. During
start up, the drum pressure is controlled to maintain R-204 inlet temperature and by
bypassing the second compartment of E-208 through temperature controller.
1.4

CO-CONVERSION

Carbon monoxide present in the reformed gas is converted to CO2 in two shift
converters R-204 and R-205. The following reaction is taking place in the shift converters
R-204 and R-205:

CO

H2O

CO2

H2

Heat

The exit gas from R-205 will contain only about 0.22 mole % CO, thereby increasing the
yield of H2. The above mentioned shift reaction taking place in the converters R-204 and
R-205 will only proceed in contact with a catalyst. The equilibrium is favored by lower
temperatures and high steam to gas ratio, while the reaction rate will be higher at higher
temperatures. More steam to gas ratio may give an apparently lower conversion due to
the larger total volume resulting in a shorter contact time. This means that for each
catalyst there will be an optimum temperature, depending on the activity and the
quantity, which will give optimum conversion. As the reaction results in a temperature
rise, the outlet gas will be at an unfavorable equilibrium if removal of heat has not taken
place before the conversion is completed. Thus the conversion is performed in two steps.
The first step takes place in the HT shift converter R-204 where a copper promoted Iron
Oxide Catalyst is installed. The major part of the conversion takes place in R-204,
causing a temperature rise of 64 oC. The outlet temperature is about 424 oC and outlet
co-concentration is 2.68 % which is fully acceptable for a conventional catalyst being
more rugged than the low temperature catalyst used in the second step of the shift
conversion. The low temperature catalyst consists of specially prepared copper, zinc and
aluminium oxides having a much higher activity, which means that it can be used at the
lower temperatures of 200 oC at inlet and 218 oC outlet. The inlet temperature is fixed
taking into consideration the dew point of the gas mixture. The catalyst is less rugged
and loses it activity if the temperatures are higher than 250 - 270 oC.Here the CO
content is further reduced to about 0.22 mole % (Dry Basis)
HIGH TEMPERATURE SHIFT CONVERSION
The HT shift converter R-204 contains 70 M3 copper promoted iron oxide catalyst. The
reformed gas enters the HT shift converter at 360 oC and 29.8 Kg/cm2g and flows

through the catalyst bed. The outlet temperature is 424 oC. At the main startup of the
plant, the catalyst must be activated, which is mainly a reduction of Fe203 to Fe304. The
reduction will take place at a temperature above 250 oC, but the temperature should not
be allowed to exceed 400 oC during the reduction in order not to decrease the activity of
the catalyst. When new, the catalyst can operate at a gas inlet temperature of 350 oC.

Afterwards, the optimum inlet temperature will be higher, but as long as the outlet
temperature has not reached 470 oC, the activity will only decrease slowly.
The cold catalyst can be heated by steam alone, both when oxidized and reduced. Drops
of liquid water on the hot catalyst may result in disintegration of the catalyst. The
catalyst is very sensitive to salts, which may be introduced with the steam. The content
of chlorine in the gas should be well below 0.1 ppm. The catalyst is not influenced by
sulphur in the quantities present in this plant. The fresh catalyst contains, however,
about 0.3% sulphate, which will be given off as H 2S during the first week of operation.
Normally the catalyst is not oxidized by steam alone, but should be oxidized by adding a
small amount of air to the steam before it is accessible as it is pyrophoric in reduced
state.

HEAT RECOVERY FROM HT SHIFTED GAS

The final shift reaction is completed in Low temperature shift converter R-205. The gas
leaving HTS is cooled to 200 oC before entering LT shift converter by recovering waste
heat successively in Waste Heat Boiler after Co-converter E-210 and BFW Pre-heater E211A/B and Trim Heater E-209. In E-210, KS steam is generated while cooling the gas to
340 oC. Part of gas is sent to the Trim Heater E-209 to preheat the Methanator feed inlet
gas partly. The gas then passes through the shell side of E-211A/B and gets cooled to
200 oC. There is a bypass of E-211A/B for controlling LT Shift Converter gas at desired
inlet temperature.

LOW TEMPERATURE SHIFT CONVERTER

The LT Shift Converter R-205 contains 80.3 M3 of the catalyst consisting of oxides of
copper, zinc and aluminium. As the catalyst is extremely sensitive to sulphur which may
be liberated not only from the preceding HT shift catalyst but also from secondary
reformer refractory material, the LT shift converter is bypassed during initial stage until
the gas is practically sulphur free. The chlorine may be present in process steam and
quench water, due to mal-operation of the water treatment system and process air due
to atmospheric air pollution in very small amounts. Besides chlorides and sulphur,
gaseous Si compounds are also catalyst poisons. When the catalyst is in a reduced state,
temperatures above 250 oC must normally be avoided. A short exposure to 300 oC will
have no adverse effect on the catalyst. Normal operation should take place at as low a
temperature as possible. How ever, at temperatures near the dew point, the activity will
decrease because of capillary condensation of water inside the catalyst, thus reducing

the free area. During operation, the temperature should, therefore, be kept at least 20
o
C above the dew point of the gas. The reduced catalyst is pyrophoric and has to be
oxidized before opening of the converter. The normal operating temperature is between
200 oC and 218 oC.
The actual temperature of the inlet gas to R-205 to be selected is dependent on the
activity of the catalyst.

1.5

CO2 REMOVAL SECTION

This unit provides process gas free of CO2 (limit 1000 ppm) for the production of
ammonia and necessary CO2 for Urea production. In this unit, CO2 in the process gas is
absorbed by the GV solution in the Absorber, C-301 thus providing process gas with less
than 1000 ppm of CO2. Stripping of the absorbed CO2 is done in the two regenerators
and CO2 stripped is supplied to Urea Plant. CO2 removal section know how is by
Giammarco-Vetrocoke of Italy. The Vetrocoke solution consists of K2 CO3, Vanadium
Pentoxide, glycine and DEA where V2O5 (Vanadium Pentoxide) is the corrosion inhibitor
and glycine/DEA are the activators. The chemistry involved in this unit is chemisorption
and is explained as follows:

CO2

H2O

HCO3-

H+

(1)

K2CO3 +

HCO3- +

H+

2KHCO3

(2)

K2CO3 +

CO2

H2O

2KHCO3

(3)

The reaction rate of (3) depends on the reaction rates of (1) and (2). Reaction rate of (1)
is slow and the activator activates this reaction by quickly introducing the gaseous CO2
in the liquid phase. The activator glycine reacts with CO2 and forms glycine carbonate
according to the reaction.

NH2 CH2 COO-

CO2

COO-NH CH2 COO-

H+

(4)

COO-NH CH2 COO-

H2O

NH2 CH2 COO-

HCO3- (5)

The sum of (4) and (5) gives (1).

In solution regeneration, reaction (3) is reversed by application of heat and pressure
reduction and the lean and semi-lean K2CO3 solution is recirculated for further
absorption of CO2. The process gas from V-208 enters the CO2 removal section at 27.5
Kg/cm2g and 165 oC and passes through the reboilers, LP Boiler (E-302) and E- 306A/B
(DM Water Heater) getting cooled down to 113.5 oC and condensate is separated in V301 before entering the absorber.
The process gas enters the tube side of E-301A/B giving its heat energy to the GV
solution at the shell side of E-301A/B. The solution from the bottom tray of C-302
(Regenerator under pressure) circulates through the reboiler by thermal siphoning. The
CO2 and H2O vapour along with solution enters C-302 bottom below the bottom tray and
serves as stripping medium. The heat energy released in E-302 shell is used to produce
LS steam, which is boosted, into C-302 through the ejectors L-301A/B. The outlet gas
temperature of E-302 is 126.5 oC. The gas outlet from E-302 is further cooled in DM

water preheaters E-306A/B. The gas is cooled down to 113.5 oC. The resulting
condensate in the process gas is separated in V-301 before entering the CO2 absorber.
In the CO2 Absorber C-301 process gas flows upwards counter current to the solution
flow (the solution is the regenerated GV solution from C-303). Semi-lean solution pumps
P-302A/B/C takes suction from the take off tray below the packing of C-303 and pumps
the solution to the middle of Absorber as semi-lean solution at 106 oC. Lean solution
pumps P-301A/B takes suction from the bottom of C-303 through the cooler E-303 and
pumps the solution to the top of the absorber as lean solution. E-303 cools the solution
from 109 oC to 65 oC and in turn heats DM water from 40 oC to 104 oC. The make up
condensate to CO2 removal system is added at the suction of P-301A/B pumps at 59 oC
to maintain the water balance in the system.
At the bottom of absorbers C-301 where the bulk of CO2 is absorbed, the high
temperature improves the reaction rate for reaction No. (3) and for reaction No. (5)
according to which the CO2 is absorbed by K2 CO3. In the top part of the absorber, the
lower temperature reduces the CO2 vapour pressure in the solution thereby minimising
the CO2 content in the process gas. This is made possible by keeping the reaction rate
(5) sufficiently high even at this lower temperature by the OH concentrations in the lean
solution fed at the top.
Solution regeneration is carried out at two pressure levels, one at 1.04 Kg/Cm 2g and
other at 0.1 Kg/Cm2g for better utilization of stripping steam compared to the usual
technique in which great part of the stripping steam exits the regenerator top as unused
excess. The pressure in regenerator C-302 is regulated to obtain a temperature increase
between the solution inlet and outlet of the regenerator in order to condense the abovementioned excess steam. The heat stored in the rich GV solution outlet of regenerator C302, is recovered as flash steam which has been experimentally verified to be practically
pure steam.
From C-302 top is taken off a rich solution stream at 106.5 oC that feeds Regenerator at
low pressure C-303. In C-303 the flashed steam regenerates the rich solution stream
taken off from C-302 top. The liquid levels at the bottom of C-303 and at the take off
tray are maintained by controlling the flow of lean and semi-lean solution from C-302.
The lean solution from the bottom of C-303 at 109 oC gets cooled in E-303 and is
pumped by lean solution pumps P-301A/B at 65 oC to the top of C-301. From the take off
tray of C-303 the solution goes to the Semi-lean pumps P-302A/B/C at 106 oC to be
pumped to middle of C-301.
The acid gas stream from the top of the Regenerator C-302 is cooled in the DM water
preheater E-307 from 102 oC to 96 oC at 1.04 Kg/Cm2 g pressure. C-302 pressure is
maintained by PIC-015. The vapour condensed is removed in V-304 (OH condensate
separator). The acid gas stream outlet of Regenerator C-303 at 94 oC and 0.1 Kg/cm 2 g
is cooled in the O/H DM water heater E-308 to 91 oC and the vapour condensed is
removed in the C-303 1st O/H condensate separator V-305. C-303 pressure is
maintained by PIC-001. Again the acid gas is cooled in the condensers E-304A/B to 40 oC
by cooling water. The vapour condensed is separated in the C-303 2nd OH condensate

separator V-302. The CO2 is fed to the Booster compressor K-301 or it can be vented to
atmosphere through PIC-026. K-301 boosts the pressure of CO 2 from 0.1 Kg/Cm2 g to
0.96 Kg/Cm2 g at 96 oC. The discharge of Booster compressor joins the stream of CO 2
from C-302 at the outlet of V-304 and the mixed stream gets cooled in the final OH
condensers E-305A/B from 102 oC to 40 oC by cooling water. The water vapour
condensed is removed in final OH condensate separator V-303 and the CO 2 saturated
with water flows to Urea Plant. The ammonia Plant battery limit conditions for the CO 2
sent to Urea Plant are 0.6 Kg/cm2g and 40 oC.
The use of compressor K-301 on a very limited acid gas stream allows to utilise in the
most advantageous way, the two pressure levels regeneration technique. Since it allows
to keep C-303 pressure at a lower level, thereby increasing the flashing steam of the
solution coming from C-302 with evident energy saving. At the same time it allows to
obtain all CO2 for Urea production at higher pressure.
The condensate separated out at V-304 and V-303 flows to V-305 and V-302 respectively
under pressure where as condensate from V-305 and V-302 are pumped out by P-304
and P-305 condensate pumps respectively as make up to CO2 removal section and
balance as process condensate to stripping unit. There are two numbers lean solution
pumps (P-301A/B) one steam turbine driven and the other motor driven. Out of three
semi-lean solution pumps (P-302A/B/C), two are steam turbine driven and the other
motor driven.
Two hydraulic turbines (DPTP-302 A/B) are connected to the turbine driven semi-lean
solution pumps P-302A/B through auto clutch. The letdown turbines sends the rich
solution from Absorber bottom, which is at a pressure of 27.5 Kg/Cm 2 g to the
Regenerator C-302 which is at a pressure of 1.04 Kg/Cm 2 g. The discharge pressure of
hydraulic turbine will be about 9 Kg/Cm 2g. The differential pressure 18.5 Kg/Cm 2 g is
utilised to drive the semi-lean solution pumps. This pressure energy approximately
amounts to a power of 215 kW in each hydraulic turbine thus energy on steam driven
turbines DSTP-302A/B is conserved to an extent of 215 kW on each turbine, by clutching
Hydraulic turbine to the Semi-lean solution pumps.
1.6

METHANATION

As CO and CO2 are poisons to the Ammonia converter catalyst, the unconverted CO and
unabsorbed CO2 in the process gas are reduced to a limit of less than 10 ppm by
methanation reaction. In the process, CO and CO2 get converted to CH 4 which is an inert
in the synthesis of ammonia. In the Methanator R-301, the reverse of reforming reaction
takes place in presence of Nickel catalyst.
The reaction formulas are as follows:
CO

3 H2

CH4

H2O

Heat

CO2

4 H2

CH4

2 H2O +

Heat

The main reason why the reaction is reversed is the lower temperature favoring
formation of methane. Other critical variables governing the reactions are pressure and
steam content. However, within the allowable temperature range, the equilibrium
conditions are so favorable that practically only the catalyst activity determines the
efficiency of the methanation. The higher the temperature, the better the efficiency, but
at the same time it means a shorter lifetime for the catalyst.
Further more in case of a possible break through of CO2 and CO to the methanator
which would result in a higher temperature rise, a low inlet temperature is preferred as
this limits the temperature rise. After the methanator the gas normally contains 10 ppm
of CO + CO2. The temperature rise of gas in methanator will normally be about 21 oC.
Methanator contains 26 M3 of catalyst and has approximately the same characteristics
as of reformer, being nickel catalyst on a ceramic base. As the reactions take place at
much lower temperature than those prevailing in the reformers, the catalyst must be
very active at low temperatures. The catalyst is sensitive to Arsenic, Sulphur and
Chloride Compounds. The adiabatic temperature rise per mole % of CO is 74 oC and per
mole % of CO2 is 60 oC. The methanation reaction starts at a temperature of about 240
o
C but in order to ensure a sufficiently low concentration of CO and CO2 in the effluent
gas, the operating temperature would be from 280 oC to 350 oC, depending on the
catalyst activity and gas composition. The methanator catalyst should not be exposed to
catalyst temperature above 440 oC for longer periods of time, as it will damage the
vessel R-301.
Washed gas from CO2 removal (outlet of V-314) goes to E-311 Gas/Gas exchanger at
26.8 Kg/Cm2 g and 65 oC and gets heated up to the inlet temperature of 310 oC by
exchange of heat with hot methanator effluent gas. A part of the outlet gas from E311A/B passes through E-209 and gets heated up with R-204 outlet gas and joins at the
inlet of methanator (resultant temperature is 320 oC. The outlet gas from methanator at
341 oC gets cooled in the Gas/Gas exchanger E-311A/B to 87.3 oC and is further cooled
down in E-312A/B (final gas cooler) to 41 oC by cooling water and the condensate
formed is separated in the final gas separator V-311. The pure synthesis gas enters syn.
gas compressor suction at a pressure of 25.1 Kg/Cm 2 g and 41 oC. Surplus syn. gas is
taken out and sent to Auxiliary boiler to be used as fuel. In case of synthesis gas
compressor trip, or prior to the startup of synthesis gas compressor, gas is vented at
PIC-074 and PIC-071 and thus front-end pressure is maintained. From the outlet of V311, the process gas is also taken as recycle H 2 to header to feed K-204 (recycle gas
compressor). This recycle H2 line is provided with HIC-003, which controls the recycle H 2
flow to header. This valve is connected to the Methanation trip signal IS-6 which closes
HV-003 on trip signal of IS-6.

NICKEL CARBONYL GAS

Nickel carbonyl gas is a poisonous and toxic gas, which may be present in R-301. Under
certain conditions, CO in the process gas reacts with the catalyst Ni to form Nickel
carbonyl gas.

4 CO

Ni

Ni(CO)4

The favorable temp. range of the formation of this gas is between 45 oC and 205oC.
Hence R-301 catalyst should never be allowed to cool in the presence of CO containing
gas. Rather it should be purged out with N 2 at the time of shut down. While heating the
catalyst with process gas containing CO, heating should be done faster in the range of 45
o
C to 205 oC.
1.7

PROCESS CONDENSATE STRIPPING SECTION

Process condensate from V-208, V-301 and V-311 contains small amounts of dissolved
CO2, NH3 and Methanol. CO2 removal section OH condensate from V-302 and V-303
contain mainly dissolved CO2. The dissolved gases in the condensate from the above
separators are to be reduced to a tolerable limit before sending it to DM Plant for further
treatment. The condensate from V-302 and V-303 at 40 oC is pumped by P- 305A/B to a
flash separator V-352, which is a packed column and operating at atmospheric pressure.
The condensate enters the vessel on the top of the packed bed. Condensate from V- 311
at 41 oC, from V-301 at 113.5 oC and from V-208 at 165 oC enters the flash separator
below the packed bed. Due to flashing mainly the dissolved CO2 and some condensate
evaporates and the vapour travel upwards coming in contact with the downward flowing
condensate (from pump P-305A/B) in the packed bed. The dissolved CO2 in the
condensate from P- 305A/B is stripped off and is vented to atmosphere. The condensate
from the bottom of the flash separator V-352 at 101 oC enters Process Condensate
Stripper C-351, which is a tray type column having 28 trays.
In the stripper, stripping of dissolved gasses is achieved by using direct LS steam at the
bottom. LS steam at 3.5 Kg/Cm 2 g and 150 oC is used as stripping steam. The purified
condensate from stripper bottom at 109 oC is cooled in the Stripped condensate cooler E351 by cooling water to 45 oC. The cooled condensate is pumped to DM plant by stripped
condensate pumps P-351A/B at 3 Kg/Cm 2 g. The vapour from the stripper top is
condensed in the condensate stripper OH condenser EA-351 A to F (Fan coolers) and
sent to Reflux drum V-351. From the Reflux drum, the non condensables are vented to
atmosphere and the condensate at 60 oC having ammonia and methanol is partly used
as reflux and balance is sent to primary reformer for mixing with Process Steam for the
recovery of H2 and destruction of methanol.
Incase the condensate stripper section is not operable or the quality of the outlet
condensate to DM Plant is poor, facilities are provided to store the OFF-SPEC process
condensate in a tank T-351. Condensate recycle pump P-354 recycles it back for further

processing. In this way Process Condensate pollution in liquid effluent is totally

eliminated.

1.8

AMMONIA SYNTHESIS SECTION

The Ammonia Synthesis takes place in the Ammonia converter R- 501 as per the
following reaction.
Iron Catalyst
N2

3H2

2NH3

Heat

The reaction is limited by the equilibrium concentration and only part of the
Hydrogen and Nitrogen can be converted into Ammonia per pass through the
Catalyst bed . The equilibrium concentration of Ammonia is favored by high pressure
and low temperature. However, reaction rate is very much enhanced by high
temperature operations. There is a compromise between thermodynamic equilibrium
& reaction kinetics. As a result there is an optimum level for the Catalyst
temperatures at which the maximum production is obtained. At higher temperatures
the equilibrium percentage (which is the theoretically highest obtainable
concentration of Ammonia) will be too low while at lower temperature the reaction
rate will be too low. The Synthesis loop is designed for a maximum pressure of 155
Kg/Cm2g and the normal operating pressure is in the range of 131-141 Kg/Cm 2 g.
The reaction temperature in the catalyst bed is 360 - 520 oC, which is close to the
optimum level. The catalyst is a promoted iron catalyst containing small amounts of
non-reducible Oxides. A considerable amount of heat is liberated by the reaction
(about 750 Kcal/Kg of Ammonia produced), and this is utilized for production of KS
steam and for preheating Boiler feed water. Only about 20% of the Hydrogen and
Nitrogen flow contained in the Synthesis gas at converter inlet is converted into
Ammonia per pass, and it is therefore necessary to recycle the unconverted
synthesis gas to the converter. The Ammonia Converter, R-501 is a Topsoe series
200, Radial Type converter with the gas flowing through the two catalyst beds in
Radial direction. The advantage of the Radial flow converter is that the pressure drop
is less. The catalytic activity of small particles is very high and the special advantage
of the radial converter is to allow the use of small catalyst particles without a
prohibitive pressure drop.
The converter contains two catalyst beds with inter bed cooling after 1st bed. There
is also a provision of cold shot injection for better control of bed temperatures. A
total of 96 M3 Catalyst of type Topsoe KMI/KMIR is used. The first bed has a volume
of 28 M3 of KMIR Catalyst and the 2nd bed contains 68 M3 of KMI Catalyst. The
KMIR Catalyst is the pre-reduced and stabilized catalyst of KMI type. Stabilisation
involves skin Oxidation of the Catalyst where it takes-up an amount of 2% (Wt) of
Oxygen. This pre-reduced catalyst is stable in air below 100 oC. Above 100 oC it will
react with air and spontaneously heats up. The catalyst is activated by reducing Iron

oxide to free Iron. This reduction is carried out with circulating Synthesis gas. The
Catalyst activity will decrease slowly during normal operation and the lifetime of
Catalyst is 8 to 10 years. This is again influenced by the actual process conditions.
Notably the temperature in the Catalyst bed and the concentrations of Catalyst
poisons in the Synthesis gas at converter inlet. Sulphur compounds and compounds
containing Oxygen such as water (H 2O), Carbon Monoxide (CO) and Carbon dioxide
(CO2) are all poisons to the Catalyst and small amounts of the catalyst poisons will
cause a considerable decrease in Catalyst activity. Part of the poisoning effect is only
temporary and catalyst activity will recover somewhat when the gas is clean again. A
certain permanent decrease in the Catalyst activity will however remain and high
concentrations of Oxygen compounds at converter inlet even for short duration
should therefore be avoided.
PROCESS CONDITIONS
Ammonia Synthesis reaction is affected by the following parameters:

Ammonia content in the feed gas

Inert gas content in the feed gas
H2 to N2 ratio in the feed gas
Reaction temperature
Circulation Rate
Operating pressure
Catalyst activity

AMMONIA CONTENT IN THE FEED GAS

A low Ammonia concentration at converter inlet gives a high reaction rate and thus a
high production capacity. The Ammonia concentration at converter inlet is dependent
on the cooling level in the refrigeration chillers and the operating pressure. At
converter inlet 4.1 % NH3 corresponds to -5 oC at a pressure of 132 Kg/Cm 2 g in the
Ammonia Separator, V-501.
INERT GASES
The Makeup gas contains 1.33% (Vol.) of argon and methane. These gases are inerts
in the sense that they pass through the Synthesis converter without undergoing any
Chemical changes. But a high concentration of inerts reduces the partial pressures of
Hydrogen and Nitrogen thereby reducing the conversion. Therefore a constant purge
of gas from the loop is maintained to keep the inerts level in the converter inlet at
about 8%. The catalyst activity decreases with the catalyst age. This can be
compensated by either increasing the loop pressure and the circulation rate or by
decreasing the inert level.

HYDROGEN/NITROGEN RATIO
By the Synthesis reaction, 3 volumes of Hydrogen react with 1 volume of Nitrogen to
form 2 volumes of Ammonia. Therefore the H 2/N2 ratio in the loop and makeup gas
must be close to 3:1. A small change in H 2/N2 ratio of the make up gas will result in a
much bigger change in the H2/N2 ratio of the circulating Synthesis gas. The H 2/N2
ratio of the makeup gas should normally be about 2.78 so that after addition of
recovered hydrogen from PGR Unit the ratio will be about 3.0. The Synthesis loop is
designed for operating at the H 2/N2 ratio of 3.0, but special conditions may make it
favorable to operate the loop at a slightly different ratio in the range of 2.5 to 3.5.
When the ratio is decreased to 2.5, the reaction rate will increase slightly (but fall
again for ratios below 2.5, while on the other hand, the circulating Synthesis gas will
be heavier. Therefore the pressure drop through the loop will increase and the
Ammonia separator efficiency may decrease, leading to increased Ammonia
concentration at the converter inlet. The H2/N2 ratio in the loop should be kept as
constant as possible. The ratio is controlled by the H 2/N2 ratio in the makeup gas
which will have to be adjusted to get desired ratio in the circulating gas. After
making any change in the H2/N2 ratio of the makeup gas sufficient time should be
allowed for the system to find its new equilibrium before making further changes.
REACTION TEMPERATURE
The temperatures in the Catalyst bed are usually in the order of 360 oC to 520 oC. At
the inlet to each Catalyst bed, a certain minimum temperature of 360 - 380 oC is
required to ensure a sufficient reaction rate. If the temperature at catalyst inlet is
below 360 oC, the reaction rate may become so low that the heat liberated by the
reaction becomes too small to maintain the temperature in the converter. And the
reaction will quickly extinguish itself if proper process adjustments (lowering the gas
circulation and / or closing the cold shot) are not made immediately. On the other
hand it is desirable to keep the catalyst temperatures as low as possible to prolong
the catalyst life. It is therefore recommended that the catalyst inlet temperature be
kept as close as practically possible to the minimum temperature without
extinguishing the reactor. The Synthesis gas entering the converter at 252 oC is
heated in inter bed heat exchanger by the hot gas coming out of the 1st bed. Before
entering the 1st bed, the temperature of this gas is controlled to about 370-380 oC
by mixing with cold shot. As the gas passes through the catalyst bed, the
temperature increases to a maximum temperature at the outlet from the 1st catalyst
bed, which is normally the highest temperature in the converter, called the "hot
spot". The temperature of the hot spot may be up to 520 oC, but should not exceed
530 oC. The gas from the 1st bed is cooled in the inter bed heat exchanger by the
main part of the cold inlet gas to the 1st bed in order to obtain a temperature of

approx. 380 oC before entering the 2nd bed. In the 2nd bed the gas outlet
temperature is about 439 oC.
CIRCULATION RATE
The capacity of the synthesis loop with regard to Ammonia production rises with
increasing circulation rate. However, the Ammonia production per cubic meter of
circulation gas which is proportional to the temperature difference between converter
exit and converter inlet, will decrease.
OPERATING PRESSURE
The Synthesis loop is designed for a maximum pressure of 155 Kg/Cm 2 g and it is
foreseen that the Synthesis loop can operate at a pressure of 142 Kg/Cm 2 g when
operating at design production rate, design inert level and design gas composition.
The actual operating pressure is not directly controlled and is dependent on the other
process conditions, notably production rate, inert level, ammonia concentration at
converter inlet, H2/N2 ratio and Catalyst Activity. The production rate increases with
rising pressure and for a given set of process conditions, the pressure will adjust
itself so that the production rate corresponds to the amount of Makeup gas fed into
the loop. The loop pressure will be increased by increasing the Makeup gas flow to
the loop, by decreasing the circulation rate, increasing the inert level or the
concentration of Ammonia at converter inlet and by changing the H2/N2 ratio away
from the optimum. The decreases in Catalyst activity will also increase the operating
pressure.
1.9

REFRIGERATION SECTION

The refrigeration section is used to liquefy gaseous Ammonia and consists of a

compressor unit, a condenser, an accumulator and number of chillers. Liquid NH 3
flows from the NH3 accumulator, V-508, to the NH3 heater E-513, which serves to
heat Ammonia sent to the Urea Plant. Then the liquid NH 3 flows partly to make up
gas chiller, E-509 partly to the 1st NH 3 chiller, E-505 and partly to the inert gas
chiller, E-511. In E-505 & E-509 the liquid NH 3 is evaporated at 6.9 Kg/Cm2g
corresponding to a temperature of 17 oC. Part of the liquid from E-505 and E-509 is
transferred to the 2nd NH3 chiller, E-506, where it is expanded to 1.9 Kg/Cm 2 g
corresponding to a temperature of -10 oC and from E-506 part of this Ammonia is
sent to the flash vessel V-503. The refrigeration compressor (K-451) compresses
vaporised NH3 from the chillers and flash vessel, which is three-stage steam driven
centrifugal compressor. The suction pressure corresponds to the pressures in the
vessel and chillers. After compression, the vapour NH 3 is condensed with cooling
water in the NH3 condensers E-510A/B and collected in the Accumulator, V-508. Noncondensables are purged and sent to ammonia absorption unit.

1.10

AMMONIA ABSORPTION

Ammonia produced in the Ammonia Synthesis Converter, R-501 is separated from

the unreacted gas mixture in Ammonia Separator, V-501. Due to high pressure and
low temperature in V-501, the loop gases are dissolved in liquid ammonia to a
certain extent depending on their respective solubility. These gases are removed
from liquid ammonia by successfully flashing the Ammonia liquid from 132 Kg/Cm 2 g
to 25 Kg/Cm2 g in the Letdown vessel V-502 and further to near atmospheric
pressure in the Flash vessel, V-503. The vapours from the Letdown vessel, V-502
which contain 15.35% (Vol.) Ammonia are sent to Ammonia Absorption unit to
recover Ammonia. While the vapours from flash vessel, V-503 are sent to
Refrigeration Compressor, K-451 and after compression along with other Ammonia
vapours from the refrigeration circuit are condensed in NH 3 condenser and sent to
Ammonia accumulator, V-508. The uncondensed gases from Ammonia Accumulator
V-508 are again cooled in Inert gas chiller E-511 for recovering some Ammonia and
the inert gases which also contain about 48.51% (Vol.) NH 3 are sent to Ammonia
absorption unit to recover balance Ammonia. The inert and Letdown gases are sent
to the bottom of Ammonia absorber, C-522 where they are contacted with water
flowing down in the packed beds. The Ammonia is absorbed in water while the gas
mixture containing H2, N2, Ar, and CH4 is sent as off gas to be burnt in Auxiliary
steam super heater, F-202. The Ammonia water mixture along with aqueous NH 3
from PGR is sent to the distillation column, C-521 where Ammonia is separated from
water. The water is again circulated to the absorber, C-522 and partly to the absorber
in PGR unit. The overhead Ammonia gases from the distillation column are
condensed in Condenser E-522 and NH3 liquid is sent to V-503.
1.11

PURGE GAS RECOVERY UNIT

In order to maintain the inerts (CH4 + Ar) concentration in the Synthesis loop at a
constant value a continuous purge is taken from the downstream of 2nd cold Heat
Exchanger, E-508 where the inerts concentration is the maximum. Typically purge
gas is about 6% of the makeup synthesis gas. If H 2 from this purge gas can be
recovered and used for NH3 synthesis, increase in Ammonia production to an extent
of 5-7% is possible without proportionately increasing the NG feed. Normally a purge
rate sufficient to maintain the acceptable inerts level in the Synthesis loop is
maintained. But, since there is a Purge gas recovery unit in NFCL, a higher purge
rate is taken during normal level. This higher purge rate reduces the inert level in the
Synthesis loop, which has a dual effect. Firstly, conversion per pass increases due to
increased partial pressure of H2 & N2. Secondly, sensitivity of Synthesis loop

operation due to CH4 slip from secondary reformer and CO slip from LTS converter is
greatly reduced. In the PGR unit cryogenic cooling in cold box separates hydrogen,
where CH4, Ar and most of N2 are condensed. So more process Air (N2 + O2) must be
introduced to secondary reformer in order to maintain H 2:N2 ratio as 3:1 in the
Synthesis loop. The increased Process Air results in greater combustion in Secondary
Reformer, which means, more CH4 slip from Primary Reformer can be allowed.
Consequently, Primary Reformer duty is decreased marginally, resulting in better
tube life and overall less energy consumption.
The purge gas is sent at 133 Kg/Cm 2 g and 13 oC to PGR Ammonia absorber C-550,
where Ammonia is absorbed in water. The Ammonia - water mixture (Aqueous
Ammonia) from absorber C-550 is sent to the Distillation column, C-521 for
separation of Ammonia. The Purge gas, which contains traces of Ammonia and water
is letdown to 70 Kg/Cm2 g and sent through the adsorption unit where molecular
sieve is used to adsorb traces of ammonia and water. The dry gas now containing
only H2, CH4, N2 and Ar is sent to the cold box where the gas is cooled to below -180
o
C where almost all the CH4 and argon and some of the N2 are condensed. The
uncondensed Hydrogen along with some quantity of Nitrogen and small percentages
of CH4 and Argon is sent back to the 3rd stage suction of the Synthesis gas
compressor, K-431.
The gases while leaving the cold box cool the incoming feed gas. The low
temperature in the cold box is maintained by the flashing of condensed CH4 to 5
Kg/Cm2 g which is removed as off gas and along with off gas from Ammonia
absorber, C- 522 is used for burning in Auxiliary Steam Super heater F-202.