INDUSTRIAL TRAINING

At
KANPUR FERTILIZERS AND CEMENT LIMITED
on
Ammonia Production
BY
RINKU PRASAD
B.TECH. (CHEMICAL ENGINEERING)
ROLL NO. 1304551024
HBTI, KANPUR

Contents

Company profile

Introduction

Hydro desulphurisation

Natural gas primary Reforming

Secondary reforming

CO Conversion

CO2 Removal

Methanation

Ammonia Synthesis

Company Profile

KFCL was commissioned in December 1969

as the name of Duncans fertilizers limited.

Now it is handed over to the Jaypee group.

Company has a turnover of Rs. 1000 crores

in the year 2010.

There are 3 Ammonia plant units and 2 Urea

plant units.

Capacity of Urea plant is 730 TPD.

Ingredient for Ammonia

To produce ammonia we require H2 and N2

H2 we get from NG and water

N2 we get from air

NG contains about 80.75%-98.39% CH4

(lean gas -98.39% , normal 98.64% , rich

gas 80.75%)

Process description

Ammonia is produced in a process known as the

Haber process, in which nitrogen and hydrogen
react in the presence of an iron catalyst to form
ammonia.

The hydrogen is formed by reacting natural gas

and steam at high temperatures and the nitrogen
is supplied from the air.

Other gases (such as water and carbon dioxide)

are removed from the gas stream and the nitrogen
and hydrogen passed over an iron catalyst at high
temperature and pressure to form the ammonia.

The process steps

1 . Natural gas reforming

3 . Ammonia synthesis

Natural

gas desulphurization

Compression

Primary

steam-natural gas

Catalytic

reforming
Secondary

reforming and air

combustion
2 . Synthesis gas Purification
CO

shift conversion

CO2

removal

Methanation

conversion of
synthesis gas to ammonia
Condensation

ammonia

of

Block Diagram of Ammonia

Plant

DESULPHERISATION

SHIFT REACTION

COMP HOUSE

REFORMING

CO2 REMOVAL AREA

AND METHNATION

SYNTHESIS

CO2 TO UREA

AMM TO UREA

Natural Gas Desulphurization

AIM : To remove Sulphur Coming with NG
(Maximum allowable Sulphur content is 0.5
P.P.M.)
Sulphur (Such as Hydrogen Sulphide (H2S),
Mercaptans(RSH), and Thioethers(R2S) is
poisionous for the Downstream Catalayst
It consists of two Steps
1 . Hydrogenation
2 . Absorption Of H2S

Desulphurization Section

Natural
Gas Feed

Natural Gas With

Recycle Hydrogen

380oC
38 Kg/cm2
395oC

Recycle
Hydrogen

Feed Gas Preheater

Sulphur
Absorber
No. 1

Sulphur
Absorber
No. 2

Hydrogenator
351oC

Hydrogenation
In this NG is brought in contact with Hydrogen at
about 3800C and passing over a cobaltmolybdenum catalyst , the reactive sulphur
compounds are transformed into H2S.

RSH + H2

RH + H2S

R2S + 2H2 2RH + H2S

R2S2 + 3H2 RH + 2 H2S

Absorption of H2S
Followings the hydrogenation
of sulphur compounds the
formed H2S is absorbed by
the zinc oxide according to
the following reaction :

ZnO + H2S ZnS + H2O

For natural gas
desulphurization 16m3 of
catalyst ZnO/Mo2O3/Cuo are
loaded in the desulphurization
converter.

Reforming Section

Desulphurized gas is converted into synthesis gas by

catalytic reforming of the hydrocarbon mixture with
steam and the addition of air.

Reactions involve in Reformer Section:

CnH2n+2 + 2HO Cn-1H2n + CO + 3H - heat

CH + 2HO

CO + 4H - heat

CO + H

CO + HO heat

Reactions take place in two steps

1.

Primary reforming

2.

Secondary reforming

How Operating Conditions

are Decided

As per LE Chaterliers principle the reaction

of reforming requires

high temperatutre conditions

low pressure conditions

optimum pressure is set around 34kg\cm 2

pressure below this suits reforming

reaction but this is not suitable for
downstream reactions

Primary Reformer

It is the most important step in the

reforming process
It cosist of a furnace
furnace is side fired
It contains 132(33*4) tubes and 45(9*5)
burners
Catalyst is filled inside the tube
Firing is done on both the sides of the tube

Primary Reformer

The desulphurized natural gas is Heated with

superheated steam over NICKEL catalyst at 7700 C to
give a gas containing hydrogen, carbon monoxide,
carbon dioxide and methane. Hydrogen is produced by
the reaction of methane with water. This gaseous
mixture is known as synthesis gas.

Reforming reaction proceeds according to the equations:

CH4 + H2O

3H2 + CO

CH4 + 2H2O 4H2 + CO2

CO

+ H2O

H2

+ CO2

Primary Reformer

Process Air
Desulphurized Gas

Composition :
Preheater
(Mole %)
Process Steam
(At Inlet of
520 C
Catalyst Tubes)
Ar 0.02
34 - 31 kg/cm2 g
CH4 79.68
Composition
CO 2 ppm of catalyst (% w/w)
1.Nickel Monoxide, NiO (17)
Primary CO2 0.24
Reformer 2.Calcium Oxide, CaO (7)
H2 4.09
3.Potassium
N2 2.54 oxide, K2O (4)
4.Aluminum
C2H6 6.48 Oxide, Al2O3 (Balance)
C3H8 2.63
C4H10 1.88
C6H12 - 0.24
Steam Carbon Mole Ratio=3/1

Secondary
Reformer

785-795oC

Composition:
(Mole %)
(At Outlet of
Catalyst Tubes)
Ar 47 ppm
CH4 12.86
CO 9.5
CO2 10.70
H2 66.20
N2 0.74
Higher HC
Neglegible

Process Gas

Primary Reformer
Composition :
Process Air
Preheater
(Mole %)
Composition:
Desulphurized
Gas
(At Inlet of
(Mole %)
Catalyst
Secondary
Steam Carbon Mole Ratio=3/1
(At Outlet of
Tubes)
Composition
of catalyst (% w/w)
Reformer
Catalyst
Process Ar
Steam
520oC
0.02
1.Nickel Monoxide, NiO (17)
Tubes)
CH4 79.68
Ar 47 ppm
2.Calcium
Oxide, CaO (7)
Primary
CO 2 ppm
34 - 31 kg/cm2 g
CH4 12.86
3.Potassium
CO2 0.24 oxide, K2O (4)
Reformer
CO 9.5
4.Aluminum
Oxide, Al2O3 (Balance)
H2 4.09
CO2 10.70
N2 2.54
H2 66.20
C2H6 6.48
N2 0.74
C3H8 2.63
Higher HC
C4H10 1.88
Neglegible
C6H12 - 0.24
785-795oC
Process Gas

Important Parameter Of
Primary Reformer

pressure inside furnace should be slightly

below atmospheric pressure around
tubes skin temp should not exceed 905 0C
otherwise tube life would be shortened
s/c* ratio is one of the most imp paramater its
kept arround 3.3 lower s/c ratio may result in
carbon formation

*s/c=steam/carbon

Secondary Reforming

The synthesis gas is cooled slightly to 735OC.

It then flows to the secondary reformer where
it is mixed with a calculated amount of air. The
highly exothermic reaction between oxygen
and methane produces more hydrogen.
CO + H2O CO2 + H2
O2 + 2CH4 2CO + 4H2
O2 + CH4 CO2 + 2H2
2O2 + CH4 2H2O + CO2

Secondary Reformer
550oC

Gas inlet
composition (mole%)
Ar 47 ppm
CH4 12.86
CO 9.5
CO2 10.70
H2 66.20
N2 0.74

791oC

1100-1200oC
30 kg/cm2 g

Catalyst
composition(%mole):
NiO = 8 10%
Al2O3 = 87 90 %
Cao = < 0.05 %

958oC

Gas outlet
composition (mole%)
Ar 0.27
CH4 0.60
CO 13.37
CO2 7.65
H2 55.61
N2 22.47

What Happens in
Secondry Reformer

temerature of gas in top part of reformer

reaches to around 1200 degree celsius
this heat is used for further reforming
methane conc. is reduced from 12.44 vol.
%(dry basis) to 0.44 vol.%(dry basis)
sr outlet temp becomes 957 degree celsius

CO CONVERSION

The gas from the Secondary Reformer contains up to

13.17 vol. % (dry basis) carbon monoxide. This is
reduced to about 0.21 vol.% (dry basis) by converting CO
to CO2 over catalysts according to the following reaction:
CO + H20 CO2 + H2

This conversion, called shift Reaction, is carried out in

two stages. The bulk of the CO is reacted over a High
Temperature iron oxide/chromium catalyst where the CO
concentration is reduced to 2.89 vol.% and the final
reduction of CO to approximately 0.21 vol. % is achieved
over a Low Temperature zinc oxide/copper oxide catalyst.

HT/LT CO Convertors
Composition (mole%)
Composition (mole%) of
of outlet stream of HT
inlet stream of HT CO
CO Converter is:
Converter is:
Ar 0.24, CH4 0.55
Ar 0.27, CH4 0.60,
CO 3.22, CO2 15.94
CO 13.37, CO2 7.65,
H2 59.59, N2 20.48
360oC
H2 55.61, N2 22.47
29.6kg/cm2
Process gas from
205oC
Reformer Section
28.6kg/cm2
HT CO
Convertor
Catalysts
composition
(mole%) which
is available in
pellet form.
Fe2O3 - 85- 95 %
Cr2O3 - 7-9 %
CuO - 1-2%
Al2O3 - 1.0%

432oC

Catalyst consist
the oxides of Cu,
Cr and Al,
Which is most
active in between
170-250oC.

Composition (mole%)
of outlet stream of LT
CO Converter is:
LT COAr 0.24, CH4 0.53
Conver
CO 0.30, CO2 18.32
tor H2 60.73, N2 19.88

Methanator trim
heater

340oC
Waste heat
boiler

205oC 227 C
BFW Preheater 1
o

160oC
BFW Preheater 2

CO2 Removal

The gas from the LT Shift converter contains up to 17.72 vol %

(dry basis) CO2. This is reduced to about 0.05% vol. by
scrubbing solution. (Benfield process). The CO2 gas is
recovered from the rich hot potassium carbonate solution by
steam stripping and subsequently used as feed for the Urea
Plants.

The absorption of CO2 into K2CO3 / KHCO3 solutions is

controlled by the reaction:
K2CO3 +CO2+H2O 2 KHCO3

Vanadium pentoxide is add in the solution, minimum 6.4%

(calculated as V+5) as corrosion inhibitor.

Methanation

The gas from CO2 Removal section cannot be used

for Ammonia Synthesis, the CO + CO2 content must
be reduced below 5 ppm to avoid the ammonia
synthesis catalyst poisoning. The Methanator
catalyst reacts the remaining carbon oxides with
hydrogen to form water and methane.

The gas is heated to about 260C and passed over a

nickel
based
methanation
catalyst
which
hydrogenates the carbon oxides to methane as
follows:

CO + 3H2 CH4 + H2O + 49.27 kcal

CO2 + 4H2 CH4 + 2H2O + 39.43 kcal

Methanation

Normally
the
above
reactions
proceed
essentially to completion. Both Methanation
reactions are exothermic, the Methanation of
CO2 causing a temperature rise of 61C for each
volume % in the feed gas, and of CO causing a
temperature rise of approximately 74 C for each
vol. %. If too high concentrations of carbon
oxides are fed to the methanator, excessive
temperatures and possibly runways will occur.
The reactions shown will tend to be reversed if a
high steam concentration is present.

300C

Methanator
Nickel based catalyst
is used here in methanator
which consist around 27%
wt Nickel. (280-420C)

Process gas for

LT CO Converter
Process gas from
HT CO Converter

Composition(%mole)
at inlet is:
Ar- 0.29, CH4- 1.08,
H2- 73.95, N2- 24.88
Synthesis gas to loop

Trim
heater

Synthesis Gas
From CO2
Gas/Gas 60C Removal Section
26.8 Kg/cm2
HE

322C
285C

90C
25 Kg/cm2

Composition(%mole)
at inlet is:
Ar- 0.29, CH4- 0.65,
CO2-0.05,CO-0.36,
H2- 74.29,N2- 24.36

Synthesis Gas Compression

Demisted gas from the syngas cooler catch

pot is compressed in two 3-stage
reciprocating compressors A and B from
21.9 kg/cm2 and 41.5C to 270 Kg/cm2
and 122.4C.

The compressed syngas is mixed with the

recycle gas (270 kg/cm2 g and 51.1C)
and fed to the converter feed oil filter
where any oil present in the gas is
removed.

Ammonia Synthesis

The synthesis reaction is:

3H2 + N2 2NH3

The presence of inert gases reduces the percentage of ammonia

actually obtained, but the variations of temperature and pressure is
similar. Thus, high pressure and low temperature give the highest
(equilibrium concentrations of ammonia).

However, at low temperature, the reaction is slower and equilibrium

is not approached so quickly. Hence there is an optimal temperature
profile for the catalyst

The other factors affecting the production rate of ammonia are

catalyst activity, space velocity over the catalyst, and composition of
converter inlet gas.

Ammonia Synthesis Cont.

(a) Catalyst activity
The

activity of the promoted iron oxide catalyst is at a

maximum about one month after its initial reduction. It decays
slowly thereafter due to the poisons, and the effects of time
and temperature. As activity is/lost, the purge from the loop
must be increased, and eventually a point is reached where it
is more economic to change the catalyst.
The

poisons usually occurring from O2, H2O, CO and CO2,

each of which is equally harmful, and sulphur compounds.
The plant is designed on the basis of 5 ppm CO + CO2
maximum in the gas to synthesis, these being the main
poisons.

Ammonia Synthesis Cont.

(b) Space Velocity and composition of Converter Inlet Gas
The

space velocity of gas through ammonia synthesis

catalyst is very important for ammonia production.
Increasing the space velocity increases the ammonia output.
At very low space velocities, the ammonia produced is
approximately proportional to the space velocity, while at
very high space velocities the output increases very little as
the space velocity is increased. Normal operating conditions
are between these two extremes.
The ratio of hydrogen to nitrogen also affects the rate of
reaction. The optimal ratio is about 3.0: 1, but this is not
critical.

Composition(mole%) at
Outlet of Ammonia
Converter
Ar- 2.11, CH4- 7.14
H2- 52.84, N2- 17.61
NH3- 20.30

Composition(mole%)
at
Startup
nlet of Ammonia
Heater
Converter
Ar- 1.82,130C
CH4- 6.18,
H2- 65.95, N2- 21.99,2
187Kg/cm
NH3- 4.06

Ammonia
Converter Synthesis

Hot
Heat
Steam
Exchanger
Boiler HE

354C270C 180C Cooler

Makeup Synthesis
Gas

Compressors

10C
178.9Kg/cm2

Composition(mole%) of
Purge Gas of Ammonia
Converter
Ar- 2.49, CH4- 8.38
Purge
H282.48,Gas
N2- 20.82
NH3- 5.82
Composition(mole%)
Ammonia
of Let Down Gas of
Separator

10C
Chiller

Ammonia Converter
Ar- 3.16, CH4- 16.12
H2- 38.06, N2- 15.76
11C NH3- 26.88

27Kg/cm2 Let Down

Gas
10C
Ammonia
Product let
(Product)
Down tank
12C of Product
Composition(mole%)
2
25Kg/cm
Stream of Ammonia
Converter
Ar- 0.01, CH4- 0.16
H2- 0.06, N2- 0.04
NH3- 99.73