Ammonia Fertilizer

Chemical Process
Technology

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Process Description In
Details
 The natural gas contain about 94% methane, 4 % nitrogen and organic Sulphur
up-to 10 ppm

 The concentration of organic Sulphur in the feed gas must be less than 0.25
ppm because Sulphur compounds may come in contact with catalyst which is
used in the process

 These compounds of Sulphur causes poisoning of catalyst and make it inactive

 Natural gas is obtained at temperature of 38 ºC and at guage pressure of 42

kg/cm²

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Ammonia Block Diagram

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Ammonia Process Flow
Diagram

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Desulphurization Of Natural Gas

 First of all it is sent to preheater where it is heated up to 399 ºC, because

desulphurization occurs at 400 ºC

 Natural gas is heated in pre heater in such a way that burners automatically
stops when its temperature reaches up to 400 ºC

 Then this hot gas is sent to hydrogenator/hydrotreater

 Hydrogen gas is introduced and organic Sulphur is converted into hydrogen

sulphide

S + H₂ H₂S (399
ºC)
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 The reaction takes place in the presence of Co or Mo as catalyst and at a
temperature of 399 c and 40 kg/cm2

 Organic Sulphur in the natural gas is present in the form of methyl

mercaptan,

 The reaction will be,

RHS + H₂ RH + H₂S ( R = CH₃

e.t.c)
 The H₂S is then removed by absorption with ZnO in the secondary

desulphurizers

H₂S + ZnO ZnS +

H₂O
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 ZnS settle down at the bottom

 The exit gas from the desulphurizer now contains 0.25 ppm or less Sulphur

and in this amount and condition it is not a catalyst poison

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Steam
Reforming
 Steam reforming is the process of cracking natural gas
 The process is divided into two steps,
1- Primary Reforming
2- Secondary
Reforming
 Primary
 Reformer
The desulphurized gas from desulphurizers is now introduced to the primary
reformer
 Primary reformer contains metallic Ni as
catalyst
 Methane in the feed gas reacts with steam to form CO and CO₂ along with
H₂

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 The following reaction will take place,

CH₄ + H₂O CO +
3H₂
CH₄ + 2H₂0 CO₂ +
4H₂
 In the primary reforming section, un-reactive methane is 9 – 10 % at a

temperature of 823 ºC

 The reaction is highly endothermic

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Secondary
Reformer
 The reaction in the primary reformer is controlled in such a way that 10% of
the methane remained un-burnt

 Air is supplied in the secondary reformer to provide necessary nitrogen for

ammonia synthesis

CH₄ + N₂ + O₂ CO₂ + 2H₂ +

N₂
 The reaction is highly exothermic and the temperature becomes 1000 ºC and

catalyst used in this process is Ni, that,s why we call this as high pressure and
high temperature plant

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 The temperature can be controlled by air supply

 The more the air is supplied the less the temperature is and vice versa

 So, we supplied fixed quantity of air in this section in order to keep the
temperature up-to 1000 ºC
 Now the methane content in gas is only up-to 0.4%

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 Now you have to remove CO and CO₂ so that we only have hydrogen and
nitrogen

 The removal of CO and CO₂ is necessary they cause poisoning to the iron
catalyst

 The removal of CO₂ is easy as compared to the removal of CO, so that,s why
CO is converted to CO2

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Shift Conversion

 The gases leaving from the secondary reformer are very hot and its
temperature is more above 1000 ºC
 Their heat is utilized to produce high pressure steam
 The pressure of high pressure steam is 110 kg/cm²
 The high pressure steam is used to run high pressure compressor
 The process of shift conversion is divided in two steps, these are
I. High Temperature Shift
Conversion
II. Low Temperature Shift
Conversion

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High Temperature Shift
Conversion
 The hot gases from secondary reformer are cooled down to the temperature
of 371 ºC after passing through waste heat re-boilers
 The reformed gas leaving the secondary reformer contains 12.7 % CO which is
then oxidized to CO₂ by the reaction with steam which is already present in
gas
 The reaction takes place at 371 ºC and reduced Fe (iron) is used as a catalyst
CO + H₂O CO₂ +
H₂
 The reaction in HTS is exothermic and temperature reaches up-to 431 ºC

 The gas now contains 3.1 % CO which is further removed in

LTS

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Low Temperature Shift
Conversion
 The gas now has temperature up-to 431 ºC and is cooled down to 242 ºC by
passing it through waste heat boilers.

 The cooled gas is then fed to LTS where it again reacts with steam in the
presence of Cu as catalyst

 After LTS the concentration of CO becomes 0.5%

 The following reaction takes place,

CO + H₂O CO₂ +

The reaction is also exothermic and temperature of gas after LTS is 255
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CO₂
Removal
 Now the gas contains 0.5% CO and 17.5 % CO₂ we have to remove CO₂ and the
process of removal of CO₂ is called “Catacarb
System”
 In this process CO₂ is absorbed by catacarb solution (potassium carbonate
solution)
 This solution contains 25 % potassium carbonate and rest are additives,
inhibitors, anti foaming agents
 Additives increases the rate of absorption , inhibitors makes the solution
corrosion resistant and antifoaming agents are used for the removal of any
foam produced
 The following reaction takes place here
CO₂ + K₂CO₃ + H₂0
2KHCO₃
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 CO₂ absorption is done in packed bed absorbers
 These beds contain rashing rings
 Gas is introduced from the bottom and cata-carb solution is sprayed from the
top of the column
 Due to rashing rings, time of contact between cata-carb solution and gas
increases and the rate of absorption of CO₂ also
increases
 The solution flows down and is called rich CO₂
solution
 From the top of the absorber the gas containing 0.1% CO₂ is released and the
CO₂ rich solution is given to stripping tower from the bottom in order to
regenerate the cata-carb solution

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Re-generation of Cata-carb
Solution
 Regeneration of catacarb solution is carried out in stripper

 In stripper, CO2 is stripped out from catacarb

solution
 The operating conditions for stripper are

I. High
Temperature
II. Low
Pressure

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Methanization

 The gas still contains a few %age of CO and CO2

 In this section they are converted to methane
 This is hydrogenation reaction and is inverse of reforming process
 Methane is not catalyst poisioning. The reaction takes place at 315 ºC and Ni
is used as catalyst
 CO + 3H2 CH₄ +
H₂O
 CO₂ + 4H2 CH₄ +
2H₂O
 It is also exothermic reaction and temperature reaches to 364 ºC

 After secondary reforming the gas contains 0.3-0.4 % methane and now it has
1.1% methane gas

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 Now the quantities of CO₂ and CO are less than 10 ppm which is acceptable
for catalyst

 After methanization the composition of synthesis gas is as follows,

 Methane 1.1%

 Hydrogen 74%

 Nitrogen rest

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Synthesis Gas Compression

 After methanization the gas pressure is 27 kg/cm₂ (guage) and temperature is

364 ºC

 Now the synthesis gas is cooled to 38 ºC and is pressurized upto 151 kg/cm²

 Gas compression is done into two steps,

 First it is pressurized to 71 kg/cm² then it is cooled down and after

pressurized up-to 151 kg/ cm² we cool down the gas between process so that
temperature may not be high

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Ammonia Conversion

 After compression the gas is fed to ammonia converter

 Ammonia converter is a reaction vessel containing a basket with four catalyst

beds

 Reduced Fe is sticked over the bed which acts as a

catalyst
 Now the gas pressure is 151 kg/cm² . When synthesis gas comes in contact

with catalyst bed it is converted to ammonia.

 3H₂ + N₂
2NH₃
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 The reaction takes place at 500 ºC
 The synthesis gas is fed from bottom that travels to the top and contact with
beds while travelling up
 The contact time is very short being not more than 30 sec

 It is an exothermic reaction and care must be made that temperature must

not exceed 500 ºC because after this temperature decomposition of ammonia
may starts as it is a reversible reaction

 The temperature is controlled by quenching with cold synthesis gas

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