Department of Chemical Engineering, NIT Hamirpur

PREFACE
Industrial training plays a vital role in the progress of future engineers. Not only does it
provide insights about the future concerned, it also bridges the gap between theory and
practical knowledge. I was fortunate that I was provided with an opportunity of undergoing
industrial training at National Fertilizers Limited, Nangal. The experience gained during this
short period was fascinating to say the least. It was a tremendous feeling to observe the
operation of different units and processes. It was overwhelming for us to notice how such a
big fertilizer company is being monitored and operated with proper coordination to achieve
desired results. During my training I realised that in order to be a successful chemical
engineer one needs to put his/her concepts into action. Thus, I hope that this training serves
as a stepping stone for me in future and help me carve a niche for myself in this field.

1|Page
Department of Chemical Engineering, NIT Hamirpur
ACKNOWLEDGEMENT
My indebtedness and gratitude to the many individuals who have helped to shape this report
in its present form cannot be adequately conveyed in just a few sentences. Yet I must record
my immense gratitude to those who helped me undergo this valuable learning at NFL Nangal.

I am highly obliged to Training and Development Department for providing me this

opportunity to learn at NFL. I have further more to thank the officers of production for
sharing their knowledge about the plant and production process. It is really great opportunity
for me by which I have learned here many practical knowledge which are usually hard to find
in textbooks.

2|Page
 Department of Chemical Engineering, NIT Hamirpur
TABLE OF CONTENT
S.NO. Topic Page No. Remarks
1) Preface 1

2) Acknowledgement 2

3) Table of Content 3

4) About NFL 4

5) Units of NFL 5

6) NFL, Nangal 8

7) Urea 9

8) Ammonia 13

9) Carbon Dioxide 20

10) Project 24

11) References 27

3|Page
Department of Chemical Engineering, NIT Hamirpur
ABOUT NFL
Introduction
NFL, a Schedule ‘A’ & a Mini Ratna (Category-I) Company, having its registered office at
New Delhi was incorporated on 23rd August 1974. Its Corporate Office is at NOIDA (U.P).
It has an authorized capital of Rs. 1000 crore and a paid up capital of
Rs. 490.58 crore out of which Government of India’s share is 74.71 % and 25.29 % is held
by financial institutions & others.
Manufacturing Plants
NFL has five gas based Ammonia-Urea plants viz. Nangal & Bathinda plants in Punjab,
Panipat plant in Haryana and two plants at Vijaipur at District Guna, in Madhya Pradesh.
The Panipat, Bathinda & Nangal plants were revamped for feed stock conversion from
Fuel Oil to Natural Gas, an eco-friendly fuel during 2012-13 / 2013-14. Vijaipur plants of
the company were also revamped for energy savings & capacity enhancement during
2012-13, thus increasing its total annual capacity from 20.66 LMT from 17.29 LMT, an
increase of 20%. The company currently has a total annual installed capacity of 35.68
LMT (Re-assessed capacity of 32.31 LMT) & is the 2nd largest producer of Urea in the
country with a share of about 16% of total Urea production in the country.
Company has a Bio-Fertilizers Plant at Vijaipur with a capacity of 600 tonnes of solid &
liquid Bio-Fertilizers to produce three strains of Bio-Fertilizers viz. PSB, Rhizobium and
Azobacter are produced.
Products
NFL is engaged in manufacturing and marketing of Neem Coated Urea, three strains of
Bio-Fertilizers (solid & liquid) and other allied Industrial products like Ammonia, Nitric
Acid, Ammonium Nitrate, Sodium Nitrite and Sodium Nitrate. The brand name of the
company is popularly known in the market as ‘KISAN’.
The company has also started production of certified seeds under its Seeds Multiplication
Program for sale under its own brand name as Kisan Beej.
Marketing setup
NFL Marketing Network comprises of Central Marketing Office at NOIDA, three Zonal
Offices at Bhopal, Lucknow & Chandigarh, 16 State & 2 UT Offices and 35 Area offices
spread across the marketing territory of NFL.
The company has 10 Soil testing laboratories (6 Static & 4 Mobile) with annual capacity
of testing around 65000 samples for Macro Nutrients and 10000 samples for Micro
Nutrients and are fully dedicated to the testing of soil health helping farmers to facilitate
balanced fertilization.
Research Centers
The company has a R&D set up at each Manufacturing Unit i.e. at Nangal, Panipat,
Bathinda and Vijaipur as well as at Corporate Office (Noida) which are primarily focused
and undertakes various innovation studies to develop new, efficient & safer processes,
value added products and suggest implementation of energy saving schemes.

4|Page
 Department of Chemical Engineering, NIT Hamirpur
Implementation of Energy Saving Schemes
The company has recently implemented various energy saving schemes such as Purge
gas recovery plant at Vijaipur-II, hooking up of old redundant Ammonia Synthesis
Converter (S-200) with New Converter (S-300) at Panipat & Bathinda Units and
additional 2 nos. cooling tower cells in Urea Plant at Vijaipur-II. The company has also
commissioned two roof top solar plants of 100 KW & 90 KW at Corporate Office, Noida
and Bathinda Unit.
Further, in order to meet the strict energy norms fixed by GoI under New Urea Policy
2015 w.e.f. 01-04-2018, though the investment is economically unviable without suitable
dispensation as sought by NFL from GoI, the company is in the process of implementing
energy saving schemes i.e. Installation of Gas Turbine Generator along with Heat
Recovery Steam Generation Unit at Panipat, Bathinda & Nangal Units with an estimated
cost of Rs. 700 crore.
The company is also going to implement energy saving schemes at Vijaipur-I & II to
further bring down the energy consumption.
New Investments
1. Bentonite Sulphur Plant of 25000 MTPA capacity at Panipat Unit with a cost of Rs. 44
crore has been commissioned on 20th December 2017
2. Setting up Di-nitrogen Tetroxide (N2O4) plant at Vijaipur Unit on Built Own Operate &
Supply basis (BOOS) for ISRO
3. R&D initiative with M/s IARI, New Delhi to design & develop an applicator & logistic
arrangement for application of Urea Ammonia Nitrate (UAN) which is envisaged to be
manufactured at Nangal Unit.
Besides above, the company is also envisaging the following investments:
1. Construction of Natural draft prilling towers at Panipat & Bathinda Units to improve
Urea prill size with estimated cost of Rs. 90 crore (Rs. 45 crore each for Panipat &
Bathinda Unit).
2. Agro Chemical plant at Bathinda for production of farm insecticides
3. Di-Ammonium Phosphate (DAP) plant of 10 LMT per annum along with Phosphoric Acid
Plant in Algeria under buy back arrangement & in Joint Venture mode with GSFC, RCF
and NMDC.
4. Seed processing plants at Indore, Bathinda and Panipat
Joint venture
NFL in collaboration with M/s EIL and M/s FCIL has formed a Joint Venture (JV) Company
as Ramagundam Fertilizers & Chemicals Limited (RFCL) to revive the old FCIL plant at
Ramagundam. The equity participation in the joint venture is 26% each by NFL & EIL,
11% by FCIL and 11% by State Government of Telangana. This plant shall have the annual
Urea capacity of 12.71 LMT. The zero date of the project is 25th September 2015 and is
targeted to be completed by end of December 2018. The project is in progress.
Manpower Position
Total manpower of the company as on 31-03-2018 was 3430 against 4068 as on 01-04-
2014.

5|Page
Department of Chemical Engineering, NIT Hamirpur
Units of NFL
NFL Panipat
About Plant
Panipat unit of NFL was commissioned on 1st Sept 1979 based on gasification technology of Feed Stock on
LSHS /Fuel Oil with the annual installed capacity of 511500 MT of Urea. Subsequently as per guidelines of
GOI, in order to reduce subsidy burden & Carbon footprint, NFL revamped the Panipat Unit on LSTK basis
for changeover of Feedstock from LSHS/FO to Natural Gas and commercial production on Gas was
commenced during Jan 2013.

SALIENT FEATURES OF PANIPAT UNIT

Installed Capacity: 511500 MTPA
Capital Investment: 338.27 Crores
Initial Commencement
September 1, 1979
of Production:
Commencement of
Production on Gas after
March 28th, 2013
Revamp:

Process
Figure 1 : NFL Panipat[1]
Ammonia: HTAS Steam Methane Reforming (SMR) Technology
Urea: Mitsu Toatsu total Recycle C Improved
Raw material: Coal , LNG/ RLNG, Power, Water
Captive Power Plant : 2 x 15 MW

NFl Bhatinda
About Plant
Bathinda unit of NFL was commissioned on 1st Oct 1979 based on gasification technology of Feed Stock
on LSHS /Fuel Oil with the annual installed capacity of 511500 MT of Urea. Subsequently as per
guidelines of GOI, in order to reduce subsidy burden & Carbon footprint, NFL revamped the Bathinda Unit
on LSTK basis for changeover of Feedstock from LSHS/FO to Natural Gas and commercial production on
Gas was commenced during Jan 2013.

SALIENT FEATURES OF BATHINDA UNIT

Installed Capacity: 511500 MTPA
Capital Investment: 349.41 Crores
Initial Commencement
October 1, 1979
of Production:
Commencement of
Production on Gas after
March 11, 2013
Revamp:

Process
HTAS Steam Methane Reforming (SMR) Technology
Ammonia:

Mitsu Toatsu total Recycle C Improved Figure 2: NFL Bhatinda[1]

Urea:
Raw material: Coal , LNG/ RLNG, Power, Water

6|Page
Department of Chemical Engineering, NIT Hamirpur
Captive Power Plant: 2 x 15 MW

NFl Vijaypur I & II

About NFL Plant
National Fertilizers Ltd, Vijaipur unit is one of the four units of M/S National Fertilizers Limited. With the
commencement of commercial production of the Expansion project the gas based unit at Vijaipur now
comprises of two 1520 ton per day (tpd) Ammonia streams and four 1310 tpd Urea streams and related
off-site facilities. The gas is being received from the HBJ gas pipe line being operated by M/s Gas Authority
of India Ltd (GAIL) another government of India undertaking. The Ammonia stream completed under the
Expansion Project can also be operated with 50 % feed of Naphtha in case of shortage of the gas supply.
The line one plants (one stream of Ammonia and two streams of Urea ) were built with a total cost of Rs
533 Crores and the cost of the Expansion Unit (one stream of Ammonia and two streams of Urea) is
estimated at Rs 1067 Crores. For both streams of Ammonia plants the consultant have been M/S Haldor
Topsoe of Den-Mark and M/S Projects Development India Ltd. (PDIL), and for all the four streams of Urea
consultant have been PDIL and M/S Snam Progetti of Italy.
In order to further reduce energy consumption & augment capacity of the Vijaipur Plant, Company has
revamped both the plants at Vijaipur as a result. The annual installed capacity of Vijaipur Units have been
enhanced by 3.40 LMT (16% in case of Vijaipur -I and 23% in case of Vijaipur-II ) with the total capacity of
the company has been increased from 32.31 LMT to 35.68 LMT.

SALIENT FEATURES OF VIJAIPUR UNIT – I

Installed Capacity: 999900 MTPA
Capital Investment: 516.00 Crores
Initial Commencement
November 1, 1988
of Production:
Commencement of April 24, 2012
Revamp:

Process
Ammonia: Steam reforming of NG / Naptha
Urea: Ammonia Stripping
Raw material: NG / Naptha, Power, Water
Captive Power Plant: 3 x 17 MW

SALIENT FEATURES OF VIJAIPUR UNIT – II Figure 3: NFL Vijaypur[1]

Installed Capacity: 1066230 MTPA
Capital Investment: 1071.00 Crores
Initial Commencement
March 31,1997
of Production:
Commencement of
July 31, 2012
Revamp:

Process
Ammonia: Steam reforming of NG / Naptha
Urea: Ammonia Stripping
Raw material: NG / Naptha, Power, Water
Captive Power Plant: 3 x 17 MW

7|Page
Department of Chemical Engineering, NIT Hamirpur

NFL, Nangal
About NFL Plant
Consequent upon the reorganization of FCI group of plants, Nangal Plant was transferred to NFL &
subsequently expansion plant of Nangal Unit was commissioned with an installed capacity of 3.30 LMT.
Further in order to sustain and enhance the company’s growth, NFL successfully revamped Urea Plant of
the Nangal Unit & Commercial Production was commissioned after revamp w.e.f. 1st Feb 2001 thus
enhances the Annual installed Capacity from 3.30 LMT to 4.785 LMT. As per guidelines of GOI, in order to
reduce subsidy burden & Carbon footprint, NFL revamped the Nangal Unit on LSTK basis for changeover
of Feedstock from LSHS/FO to Natural Gas and commercial production on Gas was commenced during April
2013.

SALIENT FEATURES OF NANGAL UNIT

Installed Capacity: 478500 MTPA
Capital Investment: 229.19 Crores
Commencement of
November 1, 1978
Production:

Process
Ammonia: KBR SMR(Steam Methane Reforming) with Purifier Technology Figure 4: NFL Nangal[1]
Urea: Technimont Total Recycle Process
Raw material: Coal , LNG/ RLNG, Power, Water

Various Production Plants at National Fertilizer limited, Nangal

 Urea Manufacturing Plant

 Ammonia and Carbon di oxide manufacturing Plant
 Steam Generation Plant
 Nitric Acid manufacturing Plant
 Sodium Nitrite and Sodium Nitrate Manufacturing Plant
 Ammonium Nitrate manufacturing Plant

8|Page
Department of Chemical Engineering, NIT Hamirpur

UREA

Figure 5: Prilled Urea particles [2], Bagged Urea[3]

INTRODUCTION:
Urea is manufactured by the reaction between Carbon Dioxide gas and liquid Ammonia
in specially designed autoclave reactors.

CO2 + 2NH3 ↔ NH2CONH2 (Urea) + H2O

The above reaction, is an typical example of Carboxylation reaction, where CO2 is weak
acid and NH3 is weak base. The overall reaction is exothermic equilibrium reaction, hence
temperature and pressure play a very important role in kinetics of the reaction. The
undesired side reaction is the formation of Biuret.

2NH2CONH2 ↔ NH2CONHCONH2 + NH3

9|Page
Department of Chemical Engineering, NIT Hamirpur
Biuret if formed when two moles of Urea react together giving Biuret and Ammonia,
typically excess Ammonia is used in order to prevent Biuret formation. Other Parameters
effecting Biuret formation are Residence time in Prilling tower and temperature of Urea
melt, also concentration of Urea solution plays a important role.

Various manufacturing processes of Urea are listed as follows:

1.Montedison total recycle process [NFL Nangal]
2.Mitsui Toatsu process [NFL Panipat & NFL Bhatinda]
3.Snamprogretti process [NFL Vijaypur]
4.Stamicarbon process

[1.] MONTEDISON TOTAL RECYCLE (Revamped by Urea Casale) Process :

The process involves two reactors, a single once through reactor (R2) and a reactor (R1)
which handles the carbamate recycle. A total Carbamate condenser is installed before
Reactor R1. There are three decomposition stages, followed by two Vacuum
concentration stages, to give a Urea melt of 99 % concentration. A natural draft prilling
tower is installed. Low pressure absorbate is used to absorb gases in high pressure stages.

Typical process parameter used in plant operation:

N/C ratio = 3 to 4
Temperature of reactor = 200 0C
pressure inside reactor = 200 to 350 ATA

Compared to other Urea manufacturing processes this process has a slightly higher
energy consumption, due to several stages of ammonia recovery and recycle. Water
content in recycle is comparatively high.

The urea plant has been divided into three main sections for operations reasons [4]:

Section 1: Urea Synthesis Section

This section comprises the synthesis loop, exiting and new items, and the three
decomposition and recovery stages working at 70, 12 and 3 ata pressure respectively.

Section 2: Vacuum Concentration Section

This section located at the top of the old prilling tower includes two vacuum
concentration stages at 0.35 and 0.04 ata respectively in order to concentrate the dilute
urea solution(about 73%) coming from the synthesis section to about 99.5% urea melt
followed by the prilling performed in the new natural draft prilling tower located
nearness the old tower.

Section 3: Ammonia Recovery Section

This section consists of the rectification column operating at about 2 ata followed by
absorption column for the NH3 recovery from the process condensates coming from the
vacuum concentration.

10 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Figure 6: Urea manufacturing process [Montedison Total recycle process][5]

[2.] MITSUI-TOATSU C IMPROVED PROCESS:

The process involves three decomposition stages or less, followed by a crystallisation section of
urea melt, the off gases from the units are absorbed in the mother liquor from the crystalliser and
recycled back to the reactor. The urea melt from subsequent stages is stripped in next
decomposition stage from the vapours. The main focus of the process is to reduce water content
in the reactor recycle stream, this is achieved by absorbing the gases in urea mother liquor from
the crystallizer, which is heated and then used for absorbing the gases in high pressure
decomposition sections instead of using low pressure stage absorbate. The overall conversion of
the reactor is thus maintained.
Typical parameters are:
N/C = 3 to 5
Reactor temperature = 250 OC
Reactor pressure = 200 to 400 ATA.
This process is little better in terms of yield and biuret content in Urea product, the energy
consumption is more or less same as the Montedison process.

[3.] SNAMPROGETTI PROCESS:

This is a total recycle process based on stripping, ammonia is used generally as stripping
agent but CO2 can also be used. The plant operates at a high N/C ratio, thus ammonia acts

11 | P a g e
Department of Chemical Engineering, NIT Hamirpur
as stripping agent. SAIPEM recommends use of Urea grade steel for reactor section and
offers different options for the stripper material, namely Zirconium and Urea grade steel
material. Now a days SAIPEM has launched OmegaBondTM material compromising
Titanium tube with extruded bonded Zirconium inner tube. The need for high pressure
pumping equipment is eliminated as the stripper and carbamate condenser operate at
the same pressure as the synthesis section. Conversion in reactor is around 60%, overall
conversion on the basis of CO2 fed can be as high as 75-80% due to carbamate
decomposition in HP section. The plant layout is horizontal.
Typical Operating Parameters:
N/C=3.3-5
Reactor temperature= 190 0C
Reactor Pressure= 160 ATA
Stripper Pressure= 160 ATA
Stripper temperature= 210 0C
The Energy savings in this process compared to the previous two process is substantially
high, nowadays new plants of more capacity are being installed using Snamprogretti.
Capacity ranging from 3000 to 3500 MTPD Urea.

[4.] STAMICARBON PROCESS:

Stamicarbon process consists of a reactor, stripper, pool condenser and scrubber in the
synthesis section. The design has been named LAUNCH MELTTM. The N/C ratio is
maintained around 3, stripping agent is CO2, and material used in the stripper is reactor
recommended by Stamicarbon is SafurexR.
Typical parameters are:
N/C = 3
Reactor temperature: 185 0C
Reactor pressure: 140 ATA
overall conversion can be as high as 80% of fed carbon di oxide. Stripper pressure is
around same as that of reactor. Stamicarbon uses a vertical plant layout hence uses
gravity for driving the carbamate solution. Stamicarbon has introduced Technology to
increase the plant capacity to 6000 MTPD. The single stream process does not have MP
decomposition section.
The process requires less energy, and is comparable to Saipem technology. The stripper
tubes consist of ferrules and top section of stripper has a packed bed, followed by a
distributor to evenly distribute the urea solution coming from reactor over the tubes,
heating is achieved by condensing steam.

12 | P a g e
Department of Chemical Engineering, NIT Hamirpur
The pool reactor has a pool of condensing liquid, which has u-tube bundles immersed in
it. Steam in generated in the tube side and the steam thus produced used in LP
recirculation section and vacuum section.

AMMONIA
Introduction:
Haber and Bosch are credited with the invention of modern day ammonia synthesis
process, they were awarded the Nobel prize for their contribution to mankind. The
process involves reaction of nitrogen and hydrogen in a high pressure, moderately high
temperature reactor, in presence of iron catalysts. The design and composition of catalyst
is quite complex. Ammonia was first manufactured by BASF plant at Oppau, Germany.
BASF researcher Alwin Mittasch is credited with inventing the iron-based catalyst.
The reaction is as follows:
N2 + 3H2 ↔ 2NH3

The reaction is exothermic with a heat of reaction around 45 KJ/mole.

Main source of nitrogen is air and source of hydrogen is natural gas, the reaction occurs
around 200 atm. pressure and 400 0C. The reaction rate constant increases with
decreasing temperature but the temperature cannot be set low as kinetics start to play
its role on the reaction.

Various manufacturing processes of Ammonia are listed as follows:

1. HALDOR TOPSOE AMMONIA PLANTS [NFL Vijaypur, NFL Panipat, NFL Bhatinda]
2. Uhde AMMONIA PLANTS
3. LINDE AMMONIA CONCEPT(LAC) PROCESS
4. KELLOG BROWN AND ROOT AMMONIA PROCESS [ NFL Nangal]

[1.] HALDOR TOPSOE AMMONIA PLANTS:

The Topsoe plant differs from other technology in the design of reformer and carbon di
oxide removal system, other steps like desulphurization, CO shift conversion,
methanation and ammonia synthesis steps are very similar.
The reformer in Topsoe plants are side fired, the reformer section is divided in two parts,
making the total number of walls four. There are six rows of burners along each wall with
9 burners in each row, since there are four walls the total burners are 216. Steam to
carbon ratio is 3.0 and methane slip from primary reformer is around 12.5%.
methane slip after secondary reformer is around 0.6%.
The air in secondary reformer is maintained so as to get H2/N2 ratio of 3.
For carbon dioxide removal Haldor Topsoe offers various choices like activated MDEA
process, Gv process, Benfield Process.

[2.] Uhde AMMONIA PROCESS:

The primary reformer in this process is top fired and it may involve one or two synthesis
converters, the main difference is in method used for carbon dioxide removal. Uhde
recommends use of activated OASE WHITE® (aMDEA®) licensed by BASF. This process
combines both effects of physical and chemical absorption. The major design difference
is use of two synthesis converters in order to maximise conversion. Large catalyst volume

13 | P a g e
Department of Chemical Engineering, NIT Hamirpur
is used, the reactors consist of three beds, two in one reactor and other reactor of single
bed, and radial flow is used. Uhde says the energy consumed is around 6.4 to 7.2 Gcal/MT
ammonia.

[3.] LINDE AMMONIA CONCEPT(LAC) PROCESS:

The process uses natural gas or light hydrocarbons for production of ammonia, Gas
purification system is PSA(pressure swing adsorption), no secondary reformer is present.
Plant capacities upto 1350 MTPD have been installed using the concept. LAC uses Casale's
ammonia radial flow converter. First plant was installed for GSFC Gujrat in 1998.
The nitrogen producing unit is separate, and nitrogen is added upstream of syngas
compressor.

[4.] KELLOG BROWN AND ROOT AMMONIA PROCESS[6]:

The process involves cryogenic purification technology named KBR PURIFIER® to
maintain H2/N2 ratio for synthesis of ammonia. The front end and Back end are thus
independent of each other because of the purifier. Primary reformer is top fired, with 3
bundles of tubes containing 44 tubes per bundle. Total four burner bundles are present
with 14 burners in each burner. Additional 4 tunnel burner are present towards bottom
of reformer; they maintain the temperature of flue gas around 1000 0C for heat recovery
and steam generation section. Steam to carbon ratio is around 2.7.
The feature of using excess air in secondary reformer shifts the load from primary
reformer thus increasing the life of tubes.

Figure 7: Kellog Brown and Root ammonia process ( KAAP plus Technology)

14 | P a g e
Department of Chemical Engineering, NIT Hamirpur
KBR KAAPplus Process a) Air compressor; b) Sulphur removal; c) Process heater; d) Automatic reformer
(ATR); e) Reforming exchanger (KRES); f) Condensate stripper; g) CO2 absorber; h) Methanator; i) CO2
stripper; j) Dryer; k) Expander; l) Feed/effluent exchanger; m) Condenser; n) Rectifier column; o)
Synthesis gas compressor; p) KAAP ammonia converter; q) Refrigeration compressor; r) Refrigeration
exchanger

15 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Figure 8: Ammonia Synthesis Catalyst ( prepared by Haldor Topsoe) [7]

The main process steps are as follows:

 Feed Gas Compression, Preheating and Desulphurisation

 Primary Reforming
 Process Air Compression
 Secondary Reforming
 Shift Conversion
 Carbon Dioxide Removal
 Methanation
 Drying
 Cryogenic Purification
 Syngas Compression
 Ammonia Synthesis
 Purge Gas Ammonia Recovery
 Ammonia Refrigeration
 Process Condensate Stripping
 Steam System
 Cooling Water System

Figure 9: Ammonia Manufacturing Process Block Diagram

Feed Gas Compression, Preheating and Desulphurisation

Natural gas for feed and fuel is supplied at the plant battery limit at 300C and 40.5 kg/cm2.
Natural gas is initially directed to a Feed Gas Knockout Drum, where any entrained
liquids(or solids) are removed. After that natural gas is compressed to 57.3kg/cm2 in the
Feed Gas Compressor. After compression, natural gas feed is mixed with a small amount
of syngas recycled from the synthesis loop which provides required hydrogen for the
downstream hydrotreater.
The mixture of natural gas and hydrogen is heated to 3710C, first using condensing LP
steam and then Feed gas coil located in the convection section of the primary reformer.

16 | P a g e
Department of Chemical Engineering, NIT Hamirpur
The hot gas enters a two step desulphurisation system. In the first step, the hot gas passes
through a Hydrotreater, which contains cobalt/molybdenum(Co-Mo) catalyst. The
catalyst ensures hydrogenation of organic sulphur compounds, if present in the feed gas,
such as mercaptans, carbonyl sulphide, to hydrogen sulphide.
In the second step, hydrogen sulphide in the feed gas is removed in two Desulfurisers.
Each Desulfurizer contains a bed of zinc oxide.

Primary Reforming:
Desulfurized feed gas is mixed with process steam from the overhead of the process
condensate stripper to give a steam to organic carbon ratio of 2.7:1 . The mixture is
preheated to about 4950C in the convection section of the Primary Reformer. The
preheated mixed feed is distributed over tubes packed with reforming catalyst and
suspended in the radiant section. Steam reforming takes place over the nickel based
reforming catalyst in the radiant tubes to form carbon monoxide, carbon dioxide and
hydrogen.
CH4 + H2O CO + 3H2
The water gas shift reaction
converts carbon monoxide to
carbon dioxide and additional
hydrogen:
CO + H2O CO2 + H2

Figure 10: Primary Reformer

Secondary Reforming

17 | P a g e
 Department of Chemical Engineering, NIT Hamirpur

Figure 11: Secondary Reformer

Hot compressed process air and primary reformer effluent are sent to the top section of
the Secondary Reformer where spontaneous combustion occurs. The resulting hot gas
mixture then flows down through a bed of nickel based reforming catalyst in the lower
section. The unreacted methane content in the gas leaving reformer is about 1.8 mol%.
In a conventional ammonia plant, the amount of process air introduced in the secondary
reformer is carefully controlled to produce a stoichiometric 3:1 molar ratio of hydrogen to
nitrogen at the inlet to the ammonia converter. In the Purifier process(KBR), about 50
percent excess air is used in the secondary reformer with the excess nitrogen being removed
in the Purifier coldbox. The excess air produces additional combustion heat for the
reforming reactions in the secondary reformer. Thus the reforming load is shifted from
primary reformer to secondary reformer. This feature lowers the primary reformer output
temperature and furnace duty.

Shift Conversion:
The cooled secondary reformer effluent is sent to the High Temperature Shift(HTS)
Converter reactor. Here, the gas flows over a bed of HTS catalyst and carbon monoxide
reactors with steam to form carbon dioxide and hydrogen via the water gas shift
reactions.
CO + H2O CO2 + H2
About 72% of the carbon monoxide is shifted to carbon dioxide in HTS converter. The gas
then sent to LTS converter at about 200 0C. Most of the remaining carbon monoxide is
shifted to carbon dioxide in the LTS.

18 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Figure 12: Shift Gas Conversion

Carbon Dioxide Removal:

The Carbon Dioxide Removal unit uses a two stage aMDEA process licensed by BASF. The
process is completely explained in later stage.

Methanation:
The vapor from the CO2 Absorber is preheated to the methanation reaction temperature,
using methanator effluent and using condensing HP steam. The preheated gas then flows
through the Methanator where carbon oxides in the gas are converted to methane by
reaction with hydrogen over a nickel catalyst. Residual carbon leaving the methanator
are less then 5ppmv(dry basis).
CO2 + 4H2 CH4 + 2H2O
CO + 3H2 CH4 + H2O

Cryogenic Purification:
Dried raw synthesis is then sent to the cryogenic purification section. The gas is cooled
and flows through the Purifier Expander, where work is removed to provide net
refrigeration duty required for the purifier. The expander effluent is further cooled and
partially condensed and enters the Purifier Rectifier at -1820C.

Figure 13: Cryogenic Purification

The operation of the purifier is controlled by a hydrogen analyser on the synthesis gas, to
maintain an exact molar ratio of hydrogen to nitrogen of 3:1.

19 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Ammonia Synthesis:
Ammonia is produced in a fixed bed, vertical converter. Makeup and recycle gas mixture
from the synthesis gas is preheated before sending to the reactor. Ammonia
concentration in the feed to the converter is about 2.76 mol%. Ammonia is synthesized
in two adiabatic beds provided with and intercooler and an aftercooler. The converter
effluent containing about 17.70 mol% ammonia is at about 4530C. It is cooled by
generating HP steam in the synloop waste heat boiler.

Figure 14: Ammonia Synthesis

Liquid ammonia is separated out from the converter effluent in the separator while the
vapor is recycled to the last stage of the synthesis gas compressor.

Ammonia Refrigeration:
The ammonia refrigeration section supplies ammonia refrigerant to two chillers: the
Methanator Effluent Chiller and the Ammonia Chiller. Ammonia refrigerant is stored in
the Ammonia Refrigerant Receiver.

20 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Figure 15: Ammonia Refrigeration

Carbon Dioxide
Carbon dioxide (chemical formula CO2) is a colourless gas with a density about 60%
higher than that of dry air. Carbon dioxide consists of a carbon atom covalently double
bonded to two oxygen atoms. It occurs naturally in Earth's atmosphere as a trace gas. The
current concentration is about 0.04% (410 ppm) by volume, having risen from pre-
industrial levels of 280 ppm. Natural sources include volcanoes, hot springs and geysers,
and it is freed from carbonate rocks by dissolution in water and acids. Because carbon
dioxide is soluble in water, it occurs naturally in groundwater, rivers and lakes, ice caps,
glaciers and seawater. It is present in deposits of petroleum and natural gas. Carbon
dioxide is odourless at normally encountered concentrations, but at high concentrations,
it has a sharp and acidic odour.

Carbon Dioxide removal processes

 Chemical absorption
 Benfield Process
 GV Process
 Catacurb Process
 MEA Process
 Physical absorption
 Rectisol (Methanol) Process
 Selexol (Dimethyl ether of propylene Glycol) Process
 Adsorptive Purification
 Pressure Swing Absorption(Zeolites)
 Physiochemisorption
 aMDEA [NFL Panipat, NFL Bhatinda, NFL Vijaypur, NFL Nangal]

Carbon Dioxide removal using aMDEA:

Carbon Dioxide (CO2) removal processes have been a vital part of purification of process
gases in Chemical Industry. In the last twenty years, or so, MDEA (Methyldiethanolamine)
based solvents have become increasingly popular as a preferred means to recover CO2
from process gases employed in Hydrogen, Methanol, Ammonia and Synthesis Gas

21 | P a g e
Department of Chemical Engineering, NIT Hamirpur
production. The technology for amine-based solvents use in CO2 removal from synthesis
gas streams is very old, and has steadily improved.

Early amine based processes used MEA (Methylethanolamine, or 2-Aminoethanol) in low

concentrations of about 20 Wt% mixed with Water (H2O). Improvements resulted in
energy savings, by raising the concentration of MEA to about 30%, and adding
proprietary corrosion inhibitors to the amine solvent, permitting the use of carbon steel
equipment in low temperature sections of the process. Newer formulations of amine
based CO2 removal solvent use MDEA as the main chemical component, with additions of
other amines to improve the solvent retention and efficiency in a CO2 removal plant. One
of the most popular solvents in Chemical Industry uses Piperazine (C4H10N2, or Pz) as a
component in the mixture, further combined with Water. A typical composition for the
solvent on a CO2 Free basis would be 3-5 Wt% Pz, 35-37 Wt% MDEA and 60 Wt% H2O. A
higher concentration of Pz improves the solvent’s removal of CO2 from Synthesis Gas
streams in chemical plants. Higher overall strength of “Total Amine” (Pz plus MDEA) also
improves CO2 removal from Synthesis Gas (Syn-Gas), but also can result in higher
equipment corrosion in the cool lean solvent sections of plant equipment, where carbon
steel is often used. Thus, there are trade-off’s in solvent composition, that result in
optimal Pz and MDEA component strength that can achieve high process performance,
while controlling equipment cost. A flow diagram for a typical CO2 Removal System
commonly used in an Ammonia plant is shown in Figure 16. Ammonia plants generate
tremendous amounts of CO2 to be removed in the manufacture of Syn-Gas, bearing
Hydrogen and Nitrogen. The Syn-Gas in Ammonia processes typically contains about 18
volume (mole) percent CO2, which must be removed to product gas purity generally less
than 500 parts per million by volume (ppm). Many such plants prefer to purify the Syn-
Gas to less than 100 ppm CO2 in the product gas from the CO2 Absorber.

22 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Figure 16: aMDEA based CO2 Removal Process

A brief description of the CO2 Removal System is as follows. Refer to Figure 1. Syn-Gas
enters the base of the CO2 Absorber (101-E) from the upstream process Condensate
Separator (102-F). Prior to that, heat exchangers exist, which have cooled the gas to about
110-140 Deg F (43-60 Deg C). Lean Amine solvent is pumped to the top of the CO2
Absorber, and flows downward, counter-current to the Syn-Gas in the column. The Rich
amine solution exits the CO2 Absorber, with recovered CO2 chemically bound and
dissolved and passes through the lean/rich solvent heat exchanger (109-C), being heated,
prior to entering the CO2 Stripper (Regenerator) columns (102-EA/EB). These columns
are equipped with reboiler heat exchangers (105-C and 111-C) to supply heat to the
solvent to remove the CO2 from the solution. The pressure of the solvent is let-down,
through the inlet valves, as the rich solution divides into the CO2 Stripper columns. The
CO2 Absorber in Ammonia plants typically operates at a pressure of 350-400 psig (24.6-
28.1 kg/cm2 g), while the CO2 Stripper column commonly operates at 8-16 psig (0.6-1.1
kg/cm2 g).

The regenerated amine solution exits the CO2 Stripper, returning through the lean/rich
solvent exchanger (109-C), being cooled, while heating the rich solution which enters the
CO2 Strippers. The sizing of this exchanger and its associated heat recovery affects the
thermal efficiency of the CO2 Removal process. After passing through further external
cooling (generally using cooling water) the lean amine solvent returns to the lean solution
pump, where mechanical work is supplied to raise the solvent pressure, pumping the
solution once again to the CO2 Absorber, in a continuously recirculating chemical
process, often referred to as a recycle process. Recycle processes are among the most
difficult to accurately model with process engineering software, often referred to as
process simulation software.

23 | P a g e
Department of Chemical Engineering, NIT Hamirpur

Project
Use and composition of Piperazine activator in MDEA
Although methyldiethanolamine, MDEA, can be activated by a number of amines,
piperazine is the most commonly used promoter in applications involving CO2 removal
from syngas, as well as from natural gas in LNG production. Because of its very low
regeneration energy, removing CO2 using MDEA alone would be preferred; however,
the reaction in solution is extremely slow and the absorption process is controlled
entirely by resistance to mass transfer in the solvent phase. Piperazine is highly reactive
with CO2 (about ten times faster kinetics than monoethanolamine) which greatly
enhances CO2 absorption rates. Yet because only relatively small concentrations of
piperazine are needed, solvent regeneration energy requirements are not much higher
than for MDEA alone.

 Introduction
In the early days of ammonia production, monoethanolamine (MEA) was commonly
used for CO2 removal from the synthesis gas using the Girbotol process. Somewhat
later, hot potassium carbonate (the Benfield, or Hot Pot process) was used, often in a
split flow configuration described as a two‐stage Benfield LoHeat process for energy
conservation. In the last 20 years, a very substantial fraction of these plants have been
retrofitted using BASF’s aMDEA process.

N‐Methyldiethanolamine (MDEA) is a tertiary amine whose amino group is incapable of

reacting with CO2. However, it is alkaline and so is an excellent sink for protons produce
by CO2 hydrolysis. Because it is non‐reactive, aqueous MDEA by itself absorbs CO2 far
too slowly to be an effective solvent for treating ammonia synthesis gas. But when
spiked with a relatively small concentration of piperazine, a diamine that reacts
extraordinarily fast with CO2, the resulting blend is an excellent solvent for treating
syngas and removing CO2 in the production of LNG.

 USING TERTIARY AMINES FOR CO2 REMOVAL

Before looking at specific chemical solvents, it is beneficial to describe the function of an
amine that is completely nonreactive towards CO2, in the CO2 absorption process, and
to give a quantitative picture of how effective piperazine ri s, amines dissociate in water
and produce hydroxyl ion:

24 | P a g e
Department of Chemical Engineering, NIT Hamirpur
RN + H2O RNH+ + OH-
The hydroxyl ion is what gives amines their alkalinity. However, CO2 does not react
with a tertiary amino group because this group lacks the mobile hydrogen necessary to
exchange for the CO2 and form carbamate. Instead, the CO2 merely absorbs into water
and hydrolyzes:
CO2 + H2O H+ + HCO-3
The liberated proton is neutralized by the amine’s alkalinity as represented by the
hydroxyl group. Thus, unless one can directly catalyze the hydrolysis reaction itself (as
can be done using carbonic anhydrase, for example), CO2 absorption rates are not
enhanced at all by reaction and will be no faster than they would be into essentially
pure water. The function of the tertiary amine then, is not to enhance absorption rates
through chemical reaction but rather to increase dramatically the capacity of the
solvent. The trouble with straight MDEA, however, is that the CO2 absorption rate is
almost always too slow for it to be used alone, except for bulk CO2 removal at high
pressure. It simply cannot be used effectively for the deep CO2 removal required for
syngas and LNG production. The CO2 reaction must be promoted, and piperazine is an
excellent promoter.

Figure 17: Piperazine Structure

Piperazine is a cyclic diamine with the structure shown above. It reacts with CO2 about
ten times faster than MEA. Its second order rate constant at 25°C, for example, is about
59,000 L∙mol‐1∙s‐1 versus MEA at 6,000 L∙mol‐1∙s‐1. This makes piperazine the most
reactive promoter of CO2 kinetics available commercially. Over the last 30 years, the
aMDEA® process, first patented by BASF in 1982, has captured the lion’s share of the
ammonia syngas purification market, and it is still used in the majority of the world’s
ammonia plants.

 MDEA Piperazine Composition

The most commonly used total‐amine strength for generic MDEA and MDEA‐based
blends is 50 wt% although, as we shall see, this is sometimes not the best concentration
to use. Figure 4 shows how the relative concentrations of piperazine and MDEA in a 50
wt% total‐amine blend affect the CO2 left in the treated gas. It is apparent from the
figure that about 4 wt% piperazine is needed to achieve < 1 000 ppmv CO2 and that 5 or

25 | P a g e
 Department of Chemical Engineering, NIT Hamirpur
6 wt% piperazine allows one to achieve in the vicinity of 100 ppmv CO2. The treating
performance is very sensitive to the concentration the piperazine additive and this is
why it is so important to monitor solution strength for piperazine content.
Unfortunately, piperazine is somewhat
volatile so its concentration tends to fall with time more rapidly than does MDEA. Plant
performance depends critically on maintaining the right concentrations of the solvent
ingredients.

Figure 18: Effect of Piperazine concentration in MDEA (Total 50 wt% amine) in CO2 level in Treated Syngas

26 | P a g e
 Department of Chemical Engineering, NIT Hamirpur

Figure 19: Effect of Solvent Temperature on CO2 level in Treated Syngas and on Solvent Viscocity

References
1. https://www.nationalfertilizers.com/index.php?option=com_content&view=arti
cle&id=81&Itemid=112&lang=en
2. https://www.stamicarbon.com/what-we-do/urea
3. https://www.indiamart.com/proddetail/kisan-urea-7034213130.html
4. National Fertilizers Limited, Nangal Urea manufacturing manual
5. National Fertilizers Limited, Nangal Ammonia manufacturing manual
6. https://www.topsoe.com/processes/ammonia

27 | P a g e