SEPARATION OF CO2 FROM SYNTHESIS GAS

USING MDEA ABSORBER IN AMMONIA

MANUFACTURE
A PROJECT REPORT
Submitted by

HUSSAIN F

21909203011

PHILIP BERNSTEIN SAYNIK

21909203028

MAHESH R

21909203308

in partial fulfillment for the award of the degree

of

BACHELOR OF TECHNOLOGY
IN
CHEMICAL ENGINEERING

SRI VENKATESWARA COLLEGE OF ENGINEERING

ANNA UNIVERSITY : CHENNAI 600 025
APRIL / MAY 2013
ANNA UNIVERSITY, CHENNAI 600025
1

BONAFIDE CERTIFICATE
Certified that this project report SEPARATION OF CO2 FROM
SYNTHESIS GAS USING MDEA ABSORBER IN AMMONIA
MANUFACTURE is the bonafide work of Philip Bernstein Saynik,
Hussain F, Mahesh R who carried out the project work under my
supervision.

Signature

Signature

Dr. R. Parthiban

Mr. C. Muthuraj

PROFESSOR AND

SUPERVISOR

HEAD OF THE DEPARTMENT

ASSISTANT PROFESSOR

Department of Chemical Engineering

Department of Chemical Engineering

Sri Venkateswara College of Engineering

Sri Venkateswara College of Engineering

Pennalur, Sriperumbudur, 602105

Pennalur, Sriperumbudur, 602105

INTERNAL EXAMINER

EXTERNAL EXAMINER

Date:

Date:

ACKNOWLEDGEMENT

Words are inadequate to express our thoughts and feeling. We

would like to take this opportunity to thank Madras Fertilizers Limited,
who readily accepted our request for Project Work training in their
esteemed company.
We wish to express our thanks to Dr. R. Parthiban, Head of the
Department, Chemical Engineering Department, for extending his
support.
We wish to acknowledge with gratitude Mr.T.Vannia Perumal,
Energy Manager, Madras Fertilizers Limited for his valuable guidance
and advise throughout the project without whom this project would not
have been a successful one.
We would also like to thank our internal guide Mr. C. Muthuraj,
Assistant Professor, Sri Venkateswara College of Engineering for his
support and encouragement throughout the duration of the project.
Finally we would like to thank our family and friends without
whose support the project would not have taken the shape the way it did.

ABSTRACT

Ammonia serves as a raw material in most of the fertilizer

industries. The project deals with the manufacture of ammonia by steam
reforming of naphtha. Carbon dioxide (CO2) which is obtained during
purification has to be removed, since this carbon dioxide acts as a poison
in the synthesis process.
The gas coming out of the reforming section contains 21.38%
carbon dioxide by volume and must be removed before sending the gas to
the compression section. An absorber is designed to absorb this gas
counter-currently by Methyl Di-Ethanol Amine (37% by volume) as
solvent introduced to the tower to reduce the outlet concentration of CO 2
to less than 500 ppm by volume.
The project is aimed at designing the absorption column,
stripping column and heat exchanger. The effect of changing
parameters like packing material, size of packing, height of packing and
retention time was also studied.

TABLE OF CONTENTS
4

CHAPTER NO.

TITLE

PAGE NO.

ABSTRACT
1.

2.

3.

4.

iv

INTRODUCTION
1.1

About Madras Fertilizers Limited

1.2

Revamp

1.3

Post-revamp

PROCESS IN MFL
2.1

Ammonia

2.2

Urea

2.3

Utilities

2.3.1 Tertiary Treatment Plant

2.3.2 Reverse Osmosis Plant

2.3.3 Captive Power

2.3.4 Environment & Pollution Control

AMMONIA MANUFACTURE PROCESSES

3.1

The Claudes Process

3.2

The Casalas Process

3.3

The Fauser Process

3.4

Kelloggs Process

10

3.5

Habers Process

10

3.6

Selection of the Process

11

AMMONIA PROCESS AT MFL

4.1

Introduction

13

4.2

Hydrogen Desulphurization Section

14

4.2.1 Primary HDS

15

4.2.2 Secondary HDS

16

Reforming Section

17

4.3.1 Adiabatic Pre-reforming

19

4.3.2 Primary Reforming

20

4.3.3 Secondary Reforming

22

4.4

Gas Purification Section

24

4.5

Shift Conversion of CO

27

4.5.1 Primary CO Converter

28

4.5.2 LT Shift Converter

29

4.6

CO2 Removal

30

4.7

Methanation

33

4.8

Ammonia Synthesis Section

35

4.9

Refrigeration

38

4.3

5.

6.

CO2 REMOVAL SECTION

5.1

Introduction

39

5.2

Various CO2 Removal Processes

40

5.3

Solvents Used for CO2 Removal

40

5.4

Advantages of a- MDEA Process

45

5.5

Consideration of Operation Parameters

46

MATERIAL BALANCE
6.1

Overall Material Balance

49

6.2

Material Balance of CO2 Absorber

50

6.3

Material Balance of CO2 Stripper

55

6.4
7.

9.

10.

57

ENERGY BALANCE
7.1

8.

Material Balance of Heat Exchanger

Energy Balance of Heat Exchanger

58

EQUIPMENT DESIGN
8.1

Design of CO2 Absorber

59

8.2

Design of CO2 Stripper

71

8.3

Design of Heat Exchanger

78

SAFETY ASPECTS AT MFL

9.1

General Safety Aspects

89

9.2

Handling Hazardous Materials

89

9.3

Safety in Use of Pressurized Vessels

90

9.4

Safety in Use of Tools and Steam Hoses

91

CONCLUSION
BIBLIOGRAPHY

1. INTRODUCTION
1.1. About Madras Fertilizer Limited
MADRAS FERTILIZERS LIMITED (MFL) is a Central Public
Sector Undertaking situated at Manali near Chennai in Tamil Nadu, South
India. MFL is an ISO-9001-2000 and ISO-14001-2004 certified company.
MFL was incorporated in December 1966 initially as a joint venture
between the Government of India and Amoco India Corporation of USA
with equity share capital contribution of 51% and 49% respectively. Now
the Government of India holds 67.55% of shares and National Iranian Oil
Corporation (NIOC) has 32.34% shares.
The MFL plant consists of production plants: ammonia, urea in
single streams and NPK in three streams, viz. NPK A train, B train and C
train. Utilities Plant is the service plant supplying treated water, cooling
water, off-site steam, instrument air, captive power and emergency power.
On November 1, 1971, MFL commenced commercial production of
ammonia, urea and NPK complex. The feedstock for ammonia is naphtha
and it is being supplied by the neighbouring M/s Chennai Petroleum
Corporation Limited (CPCL)
The MFL plant has been in operation for the last 40 years. The
proposals for revamping and modernization of MFL plant were sent to the
Government of India for approval which was approved at an estimated
8

cost of Rs.3143 million. The revamping and modernization project of

MFL increased the economic life of the plant by 15 years and the energy
consumption down below 10 million KCal per ton of ammonia which was
as high as 14 million KCal per ton of ammonia.
In 1991, the old Chemico converter of ammonia plant was replaced
with the latest S-200 radial converter. This lead to an increase in the
production capacity of ammonia fertilizer by 50% from 7 lakh to 10.5
lakh ton per annum.
These products are marketed under the brand name Vijay. MFL
has been in production for last 25 years and during the year 1995-96 it
registered sales over 680 million ton. The net profit of Rs.21.07 trillion
completed the expansion programme of MFL. It increased the production
capacity of ammonia from 750MT/day to 1050MT/day and urea from
885MT/day to 1475MT/day.
Sewage water reverse scheme in two phases has taken off at a cost
of Rs. 260 million. The first phase of unit at Kodungaiyur is for primary
treatment of sewage, using reverse osmosis system. This reduces the
salinity in the sewage water. This water then undergoes biological and
physiochemical treatment at the tertiary treatment plant.
The original ammonia / urea plants were of Chemico design with
the daily rated capacity of 750 MT (247500 MTPA) and 885 MT (292000
MTPA) respectively. Initially there were only two trains to produce
9

granulated complex fertilizers with a total installed capacity of 360000

MTPA. In September 1976, NPK stream, namely C train was added
raising the installed capacity to 540000 MTPA.
1.2 Revamp
In order to extend the economic life of the plants by another 15
years and also envisaging improvement in energy consumption, the
company undertook a major Revamp-cum-Modernization and Capacity
Enhancement of its plants at a cost of Rs. 6 trillion during 1993-1998.
Production from the Revamped Plants commenced from March 3, 1998.
Process License and Basic Engineering from M/s Haldor Topsoe,
Denmark for ammonia plant and from M/s Urea Technologies Inc., U.S.A
for urea plant were adopted with modern Distributed Control System
(DCS). The enhanced production capacities are 1050 MTPD for ammonia
(346500 MTPA) and 1475 MTPD for urea (486750 MTPD). With respect
to NPK, Pipe-reactor with Process License & Basic Engineering from M/s
Grande Parroise, France was incorporated in NPK B train. By this and
along with higher on-stream efficiency, the installed capacity was raised to
2550 MTPD (840000 MTPD).
1.3 Post-revamp
After overcoming initial teething troubles, the ammonia & urea
plants reached 87% and 83% capacity utilization levels in 1999. To
10

improve product quality and bring down product temperature before

admitting into bagging streams, prill tower modification was carried out
by Monsanto Enviro-Chem (MECSI), U.S.A and a fluidized bed cooler
(Prills Cooling System) was put into service.
Urea plant achieved a record production of 473363 MT in 2006-07
surpassing the previous best of 473032 MT in 2004-05. Specific
consumption of feedstock has also come down over the years after process
stabilization.

11

2. PROCESS IN MFL
2.1 Ammonia
Ammonia, a chemical compound of nitrogen and hydrogen is
produced using naphtha, steam and air. Feedstock naphtha is the source of
hydrogen and atmospheric air is the source of nitrogen.
Naphtha is desulphurized in two stages and the hydrocarbon is
reformed together with steam and air to raw synthesis gas in the reforming
section. The reforming section consists of pre-reformer, primary reformer
and secondary reformer. Air is introduced into the secondary reformer.
Reformed gas containing H2, N2, CO and CO2 and minute amount of
unreformed methane (CH4) is sent to the CO shift conversion section
where CO is converted into CO2 in two steps. CO2 is absorbed using
methyl di-ethanol amine.
MDEA is removed in the CO2 removal section and the CO2 is sent
to the urea plant as one of the raw materials for its production. The
remaining CO and CO2 from the process gas are converted to CH 4 in the
methanator. The processed synthesis gas is compressed and sent to the
catalyst converters (S-200 and S-50) where ammonia is produced by the
catalytic action. Synthesized ammonia is separated and sent to urea plant
as raw material and the remaining quantity is refrigerated and stored in
cylindrical storage tanks.
12

2.2 Urea
Urea is produced by the action of ammonia with carbon-di-oxide
(obtained from ammonia plant) in stainless steel lined reactors at 215-220
kg/cm2 gauge pressure, using the technology of UTIs Total Heat Recycle
Process. The high efficiency reactor has conversion of about 76% per
pass. After flashing and decomposition at medium pressure, additional
CO2 is injected into the medium pressure system followed by flashing and
decomposition at low pressure and then concentration of urea solution at
vacuum. Further concentration takes place in the prilling tower.
Here the hot urea solution is sprayed down in a 210 cylindrical
concrete prilling tower, counter current to a stream of cold air with a free
fall height of prills for 170. The urea solidifies into small urea prills. The
prills are then passed through a fluidized bed cooler (Prills Cooling
System) to reduce the temperature and fines thereby improving the quality
of the product. The entire off gas is absorbed in a bubble cap tray absorber
and then recycled to the reactors. The chloride-free effluent is treated in a
Hydrolyser Stripper and the contents are recycled fully. The treated water
is used for demister washing. The product is sent though a system of
conveyors and elevators to bagging streams. There it is bagged and
shipped as urea product.

13

2.3 Utilities
MFL receives water from Panjetti Well-fields & Tamaraipakkam
though the Chennai Metropolitan Water Supply & Sewerage Board
(CMWSSB), which also supplies Secondary Treated Sewage Water. Water
requirement is around 3.5 IMGD. Tamil Nadu Electricity Board is the
source of electrical power supply.
2.3.1 Tertiary Treatment Plant
After experiencing acute water shortage, MFL commissioned
Tertiary Treatment Plant (630 Nm3/h Capacity) for treating the Secondary
Treated Sewage Water supplied by CMWSSB in September 1992. Tertiary
treatment of the secondary treated domestic sewage is done in two steps at
MFLs sewage reuse facility. They are Biological and Chemical treatment.
The biological treatment employs the conventional activated sludge
process with surface aerators. The chemical treatment involves the water
treatment step and finally breakpoint chlorination which kills micro
organisms and removes the last traces of ammoniacal nitrogen. The
tertiary treated water is pumped for further desalination to the Reverse
Osmosis Plant. The TTP receives Sewage Water to the tune of about 71%
of the total water requirement of plant thereby contributing to save the
precious ground water.

14

2.3.2 Reverse Osmosis Plant

The tertiary treated water is sent for chemical pre-treatment and
pressure delivered to reverse osmosis trains with permeable membrane
units. Reverse Osmosis Plant has got three streams of 160 m 3/h capacities
each.
2.3.3 Captive Power
Two different genres of Captive Power Generations 2 nos. of Gas
Turbine Generators (2.32 MW each) with Heat Recovery Systems (HS)
and 8 nos. of Diesel Gen sets (0.8 MW each) both fuelled by high speed
diesel (HSD) were installed in the year 1983 and 1991 respectively.
2.3.4 Environment & Pollution Control
Effluent treatment systems, Hydrolyser Stripper for treating
ammonia/urea effluents and Effluent Treatment Plant for liquid effluents
from NPK Plants, are in place as part of environment protection /
pollution control measures in tune with our environment policy. A
demister system is provided at the top of the urea prilling tower to reduce
the quantity of entrained urea in the air stream leaving the Evaporators
and the Prilling Tower. Cooling Water Blow-down Treatment Plant was
commissioned in March 2004 which is both a pollution abatement
mechanism and cost saving though water recycling.

15

3. VARIOUS PROCESSES IN AMMONIA MANUFACTURE

3.1 The Claudes Process
The process departs from the Habers process more than any other
ammonia synthesis process. A large amount of heat evolved in operating
at space velocities of 10000 with as much as 40% of hydrogen and
nitrogen mixture converted into ammonia in one pass in a special
converter design. In the original process, Claude used hydrogen purified
by fractional distillation of coke oven gas and nitrogen from the
liquefaction of air.
3.2 The Casalas Process
A pressure of around 500 to 900 atm is used in this process which is
otherwise distinguished by the method used for controlling catalyst
temperature in the specially designed converter. This method involves recirculating gas around a synthesis loop, similar to the Haber process
where liquefaction of the gas is attained by water cooling. The basis for
the heat control of the catalyst is to convert these by slowing down the
rate of formation of ammonia and eliminating excessive heating of the
catalyst.
3.3 The Fauser Process
This process incorporates features not previously mentioned.
Electrolytic hydrogen from fauser cells and nitrogen from liquid air units
16

or from a purification unit utilizing tail gases from absorption towers in

the ammonia oxidation plant are used. The mixture of hydrogen and
nitrogen is compressed to 200-300 atm and after processing though an oil
separator goes to oxygen contained in the gas mixture combines in a
cooler and removed in water separator.
3.4 Steam Reforming Process (Kelloggs Process)
About 50-80% of world ammonia production is from steam
reforming process and approximately 50-70% of the feed for ammonia
manufacture is natural gas. The feed stock ranging from natural gas to
naphtha is first desulphurized then mixed with steam and containing the
required amount of N2 for synthesis is introduced in the secondary
reforming step. The reformed gas is then shifted and scrubbed for methane
and water in a Methanation step.
3.5 Habers Process
The Nitrogen Engineering Corporation System using this process in
similar plants has been built in many countries. The ammonia
concentration in the circulating gas leaving the catalyst is 10 to 14 mole%.
In the condenser, ammonia concentration is reduced by condensation to
equilibrium at the exit temperature of the condenser. The condensed
ammonia is separated from the circulating compressor.
3.6 Selection of the process
17

Haber Bosch process is one of the new modern technologies. The

Haber Bosch process consumes about 20% less energy when compared to
other processes.
All the major ammonia manufacturing plants are modification of
Habers process. In this process the temperature is between 500 and
550C and a pressure of 200 to 350 atm is applied. Thus synthesis gas
must be compressed to about 200 to 350 atm. Converters contain several
catalyst layers. The catalyst is promoted iron catalyst and nickel as a
promoter is basically the same as that developed by Habers process.
About 8% volume of the synthesis gas is converted into ammonia. The
high pressure gas mixture is cooled from a temperature of 550C to about
250C by the feed gas in the lower part of the reactor and is further cooled
by water to 25C. The liquid ammonia gets separated in the separator. The
gas mixture leaving the top of the separator is returned to converter.
Advantages:
1. Low energy consumption
2. Low operating cost
3. Easy removal of sulfur due to its presence in smaller
amount.

18

Figure 4.1 Manufacture of Ammonia by Haldor Topsoe Process

19

4. AMMONIA PROCESS AT MFL

4.1 Introduction
In MFL, HALDOR TOPSOE method is currently being used for the
manufacture of ammonia. Naphtha is got from Chennai Petroleum
Corporation Limited (CPCL) and is stored in large tanks of diameter 12
meters. Each tank is covered by a floating roof which is attached to guide
pipe and the circular floating roof is scaled to the storage tank by foam
seal. Naphtha is the source of hydrogen and atmospheric air is the source
of nitrogen used in manufacture of ammonia.
Ammonia is produced from a mixture of hydrogen (H 2) and
nitrogen (N2), where the ratio of H2 to N2 should be 3 : 1. Besides these
two compounds the mixture also contains inert gases like Argon (Ar) and
Methane (CH4) to a limited extent. For the ammonia plant in Madras
Fertilizers Limited, the source of H2 is steam and hydrocarbons in the form
of naphtha. The source of N2 as in all ammonia plants is atmospheric air.
The processes which are necessary for producing ammonia from the
above mentioned raw materials are as follows
1. Hydrocarbon feed is completely desulphurized in the
desulphurization section.
2. The desulphurized hydrocarbon is reformed together with
steam and air to produce raw synthesis gas. This gas contains
20

hydrogen (H2) and nitrogen (N2) as well as carbon monoxide

(CO) and carbon dioxide (CO2) and minor amount of argon
(Ar) and unreformed methane (CH4).
3. CO is converted into CO2 in two steps. In the shift conversion
unit the remaining CO is converted into CO2 with air. The
bulk of the CO2 is removed in the MDEA unit and the
remaining CO and CO2 is converted into CH4 in the
Methanation section.
4. In the ammonia synthesis section the purified synthesis gas,
after compression to a pressure of about 200 kg/cm2 g, is
converted into ammonia by a catalytic reaction.
4.2 Hydrogen Desulphurization Section
The raw naphtha which is used as feed contains up to 0.12 wt%
sulphur. Since it is a poison to the catalysts used in reforming and
ammonia manufacture sections, it has to be removed to a very low level
before the feed is passed on to the reforming section. The removal of
sulphur is done in two steps:
1. Primary desulphurization, where the bulk of the sulphur is
hydrogenated to H2S and removed by a stripping process.
2. Secondary desulphurization, where the remaining sulphur is
hydrogenated to H2S and absorbed on a zinc oxide catalyst.
21

4.2.1 Primary Hydrogen Desulphurization

Raw naphtha feed is pumped by the raw naphtha pumps from
storage to the unit and is heated up in the naphtha heat exchangers and in
the fired heater to 340C before entering the primary HDS vessel which
contains 12.5m3 of a Cobalt Molybdenum based catalyst as 5mm rings.
The following typical reactions take place:
R- SH + H2 R H + H2S
R1- S S R2 + 3H2 R1 H + R2 H + 2H2S
R1- S R2 + 2H2 R1 H + R2 H + H2S
R = S + 2H2 R 2H + H2S
where, R is a radical of hydrocarbon.
The hydrogen is obtained by recycling purge gas which is obtained
from the ammonia synthesis section. Besides the above-mentioned
hydrogenation of sulphur compounds, the catalyst also hydrogenates
olefins to saturated hydrocarbons. The reaction mixture is cooled in
exchangers and the hydrogenating gas is separated from the naphtha. The
stripping of dissolved H2S is performed in the HDS stripper operating at 7
kg/cm2g and a temperature between 150C and 80C.
The pre-desulphurized naphtha containing about 10 ppm of H2S is
pumped by the stripper bottom pumps to the secondary desulphurization
unit. The optimum temperature range for hydrogenation is 340 - 400C.
22

At temperatures below 340C the hydrogenation reaction will not

be complete, and at temperatures above 400C, polymerization products
can be formed on the surface of the catalyst.
The activity of the sulphide catalyst is higher than that of the
oxidized catalyst, and it is therefore often advantageous to sulphide the
catalyst during the initial start-up in order to secure a maximum activity.
The catalyst will pick up sulphur to about 6 wt% when fully sulphide. In
the sulphide state the catalyst is pyrophoric at temperature above 70C,
and it should not be handled before it has been cooled down to ambient.
4.2.2 Secondary HDS
If the sulphur content in the naphtha to the secondary HDS vessel is
very low, below approximately 2ppm, for a prolonged period, sulphur will
tend to be stripped off the hydrogenation catalyst. A reduction to metals of
the Co-Mo system in the catalyst may take place. In these circumstances
there is a risk that exothermic hydrocracking reactions may occur. The
naphtha feed from the primary HDS unit is to contain minimum 2-3 ppm
H2S. During normal operating condition the sulphur content in the naphtha
will be removed in the secondary HDS down to below 0.02 ppm H2S.
Naphtha feed is mixed with hydrogen gas from the 1st stage of the
synthesis gas compressor and the mixture is evaporated and heated to
350C in the steam fired HDS preheater. In the secondary HDS unit, a
direct fired secondary HDS preheater is used.
23

The secondary desulphurization unit consists of a secondary HDS

vessel and a sulphur absorbent vessel. The first reactor containing Co-Mo
based catalyst of 5 mm size rings. The gas mixture outlet passes over the
ZnO catalyst 18.8m3, 4 mm extrudes, which will absorb H 2S according to
the reaction:
ZnO + H2S ZnS + H2O
Zinc Sulphide is not pyrophoric and no special care during
unloading is required.
4.3 Reforming Section
In the reforming section the desulphurized naphtha is converted into
raw ammonia synthesis gas by catalytic reforming with steam and
addition of air.
The steam reforming of hydrocarbons can be described by the
following reactions:
CnHm + nH2O nCO + (m/2 + n) H2 Q

(1)

CH4 + H2O CO + 3H2 Q

(2)

CO2 + H2 CO + H2O Q

(3)

Reaction (1) described a total conversion of higher hydrocarbons into CO

and H2. Methane is reformed to CO and H2 according to reaction (2).
Reaction (3), the shift conversion reaction which is an exothermic
reaction, requires a small amount of heat only, whereas the heat required

24

for (1) and (2) is to be supplied continuously for the reaction to proceed
on.
The reactions take place in three steps, in the pre reformer and the
two reformers, the primary reformer and the secondary reformer. Heat is
required for the reaction in the pre reformer as the net reaction is slightly
endothermic. The necessary heat of reaction for the two reformers is quite
different. In the primary reformer, heat is supplied indirectly by firing. In
the secondary reformer the heat is supplied as reaction heat by mixing air
into the gas. The burning gas provides heat for the rest of the reforming.
The reforming taking place in the primary reformer is adjusted in such a
way that the air supplying the reaction heat in the secondary reformer will
give the required hydrogen to nitrogen ratio of 3 : 1 at the outlet from the
methanator.
It is desirable to reduce the methane content in the raw synthesis
gas to maximize the production of hydrogen and to keep the level of inert
gases in the synthesis gas low. The methane content in the raw gas is
governed by the equilibrium of the reforming reaction (2) and by the
approach to this equilibrium obtained in practice. The equilibrium for
reaction (2) is so that higher temperature, more steam and lower pressure
results in lower methane content. On the other hand, by raising the
reforming pressure, a considerable saving in the power consumption for
synthesis gas compression can be obtained and the equipment can be

25

made smaller. An operating pressure of 30 to 35 kg/cm 2 g for the

reforming section has been found to give a reasonable economic
compromise. In order to compensate for the unfavourable equilibrium
conditions thereby encountered, a steam to carbon ratio of 3.3 has been
chosen.
4.3.1 Adiabatic Pre-reforming
As the process feed has a high content of higher hydrocarbons, it is
passed though the pre-reformer before being sent to the primary reformer.
Before the process feed enters the pre-reformer, process steam is added at
a steam/carbon ratio of 3.3 and the mixture is heated to 480C in the
process feed preheating coil located in the flue gas duct. The pre-reformer
is simply an adiabatic chemical reactor, containing 18.2 m 3, 4.3 * 4.3 mm
rings of a special reforming catalyst, which has a good reforming activity
at low temperatures, well below the kinetic limit for carbon formation.
All higher hydrocarbons will be completely converted, irreversibly,
by the first reaction while the other two reactions will be almost
equilibrated, i.e. to approximately 52 mol% CH 4 and 0.5 mol% CO (dry
basis). The gases leaving the adiabatic pre-reformer at approximately
500C is passed directly on to the primary reformer.
4.3.2 Primary Reforming

26

The primary reformer is constructed as a duplex furnace, where

each radiant chamber contains a single row of 92 (totally 184)
centrifugally cast tubes, each 11.4 m long, made of Cr-Ni steel and is
loaded with Topsoe steam reforming catalyst. The reforming catalyst is
characterized by high activity due to high nickel surface area and high
thermal resistance. Thermodynamically carbon formation is not possible
when operating the primary reformer at the chosen conditions but if the
catalyst loses activity, due to poisoning (sulphur), mal operation or aging,
carbon formation may occur. Carbon formation itself decreases the
activity of the catalyst and therefore it is very important to take immediate
action to prevent carbon formation. Carbon deposits normally increase the
pressure drop across the reformer and it may be detected by observing hot
bands on the reformer tubes. Another consequence of carbon formation is
that the catalyst particles lose their mechanical strength.
If the hydrocarbon feed has a high content of olefins, aromatics or
naphthenes, it may cause carbon formation. Furthermore, it is important
not to operate the reformer with too low steam to carbon ratio, as this
gives a thermodynamically possibility for carbon formation, especially
inside the catalyst particles. After a slight poisoning, the activity is reestablished by operating the reforming for a few hours with pure gas. A
severe sulphur poisoning requires a special regeneration procedure. Also
salt droplets in steam, for instance NaCl and Na 3PO4 and compounds
containing heavy metals are poisonous to the catalyst. For this sort of
27

poisoning, no regeneration will work. The gas leaves the tubes and enters
the refractory-lined cold collector though the bottom hairpins and hot
collectors. At the tube outlet the process gas has a temperature of about
800C. The methane concentration is about 9.5% by volume (dry basis) at
outlet.
When passing the catalyst in the tube, the following reactions take place:
CH4 + H2O CO + 3H2 Q

(2)

CO + H2O CO2 + H2 + Q

(3)

Both reactions will be close to equilibrium at the outlet temperature.

To compensate for the strongly endothermic reforming reaction (2)
the tubes are heated by 288 burners located in each side wall and arranged
in 6 horizontal rows at different elevations to provide easy control of a
uniform temperature profile along the length of the catalyst tubes. In this
manner the optimum utilization of the expensive high alloy tubes is
obtained and the risk of local hot spots is minimized. The flue gas outlet
temperature is about 1020C. The burners are of the forced draught type
operating with preheated combustion air at about 360C. In order to
ensure complete combustion of the fuel used in the burners, they are
operated with an 10% excess of air which corresponds to 2.0% by volume
(dry basis) of oxygen in the flue gas.

28

Fuel gas from the primary HDS and purge gas from the synthesis
section are mixed and preheated to 200C in the steam fired fuel gas
preheater. The remaining fuel being raw naphtha is vaporized and heated
to 200C in the steam fired naphtha fuel preheater before being sent to the
primary reformer burners. The flue gas from each radiant chamber is
collected in the flue gas collector of the flue gas heat recovery section
where the sensible heat of the flue gas is utilized, in consecutive order,
for:
1. Preheating of process feed
2. Preheating of process air
3. HP steam superheating
4. Combustion air preheating
The heat recovery section brings down the temperature of the flue gas to
about 175C. After the heat recovery section the flue gas fan leads the gas
to the stack.
4.3.3 Secondary Reforming
Preheated air at 550C is mixed into the partly reformed gas and
reacts in the upper empty space of the secondary reformer. The reaction
here is mainly a combustion resulting in a temperature rise. From the
empty space the gas passes the catalyst bed in the lower part of the
reformer where the reforming reaction is completed with simultaneous

29

cooling of the gas. The outlet temperature will be about 970C and the
methane concentration approximately 0.3% by volume (dry basis).
The exit gas from the secondary reformer contains about 14 mol %
CO and 10 mol % CO2. Consequently there is a theoretical risk of carbon
formation according to the Boudouard reaction
2CO CO2 + C (as soot)
When the gas is cooled at the actual operating conditions the carbon
formation can only take place at a temperature below 720C in the
primary reformer and below 766C in the secondary reformer, because of
the equilibrium conditions. The lower limit for the reaction is 650C as the
reaction rate becomes too slow at lower temperature. Consequently, it is
important to pass the temperature range from 766C to 650C reasonably
quickly, and also contact between gas and hot metallic surfaces is to be
avoided.
The cooling of the process gas is carried out in the waste heat
boiler, where the exchanged heat is used for producing saturated high
pressure steam at 45 kg/cm2 g being needed in the ammonia plant. The
boiler is designed to obtain the rapid cooling, but very high flux is to be
avoided, as it may cause film boiling on the steam side which in turn
would decrease the heat transfer coefficient significantly.

30

The secondary reformer has been charged with a total of 30.1 m 3 of

catalyst. The dimensions of the catalyst are 20 mm 18 mm high, with
seven holes. The catalyst bed rests on a layer of alumina lumps and on top
of the catalyst bed, a layer of alumina lumps and alumina tiles protects the
catalyst from agitation and direct flame contact. The catalyst activation is
carried out simultaneously with activation of the primary reformer
catalyst. The combustion of the process gas with air gives a gas
temperature of 1100 1200C in the upper part, but as the reforming
reaction of methane absorbs heat, the outlet temperature of the secondary
reformer is approx. 970C. In the temperature range of 1400 1500C, the
catalyst starts sintering. The activated catalyst must never be exposed to
air at temperature above 100C, as this will cause spontaneous heating,
which due to the snow balling effect may lead to overheating and
destruction of the catalyst.
4.4 Gas Purification Section
The gas leaving the reforming section has the following
composition expressed in % by volume (dry basis)

31

Table 4.1 Composition of gas leaving reforming section

Component

Mol formula

Volume Percentage

Hydrogen

H2

52.86

Carbon monoxide

CO

14.40

Carbon dioxide

CO2

10.15

Nitrogen

N2

22.02

Argon

Ar

.27

Methane

CH4

.30

Furthermore, the gas contains so much water vapour that steam to

dry gas ratio is about 0.59. Of the above compounds argon (Ar) has not
yet been mentioned. Argon is an inert gas introduced with the process air
which always contain 0.94 vol% Ar.
The purpose of the gas purification section is to prepare a
synthesis gas containing hydrogen and nitrogen in the ratio of 3 : 1 and
besides this it only containing inert gases such as methane and argon in
very low concentrations. When leaving the secondary reformer the gas
temperature is around 970C. Before entering the shift converter it is
cooled in the waste heat boiler, and in the HP BFW preheater, to 360C.
Carbon monoxide is converted according to the following reaction:
CO + H2O CO2 + H2 + heat

32

The reacted gas will contain only about 0.12 % CO by volume (dry
basis). The reacted part of the CO increases the H 2 yield with
simultaneous formation of CO2 which is more easily removable. A further
reduction of the CO content in the process gas is takes place in the
selectoxo unit, where CO reacts with O2 (from air) to form CO2. The CO2
is then removed in the CO2 removal unit leaving less than 50 ppm by
volume (dry basis) of CO2 in the gas.
Even small amounts of CO and CO2 left are severe poisons to the
ammonia synthesis catalyst and should therefore be removed down to a
concentration of few ppms. This is done in the methanator where reverse
of the reforming reaction will take place resulting in the formation of
methane at the expense of hydrogen.
CO + 3H2 CH4 + H2O + heat
CO2 + 4H2 CH4 + 2H2O + heat
In the ammonia synthesis loop the inerts Ar + CH 4 will be built up
to a level depending on how much gas is purged from the loop. The
purpose of this is to keep the methane concentration reasonably low as
nothing can be done to decrease the content of the other inert gas, Argon.

4.5 Shift Conversion of CO

33

The shift reaction taking place in the converters will proceed only
when process gas comes in contact with a catalyst.
CO + H2O CO2 + H2 + heat
The equilibrium is favoured by lower temperature and more water
while reaction rate will be higher at higher temperatures. More water may
give an apparently lower reaction rate 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, this will give optimum conversion. As the reaction results in a
temperature rise, the outlet gas will be at an unfavourable equilibrium if
removal of heat has not taken place before the conversion is finished.
Thus, the conversion is performed in three steps. The first step takes
place in the primary CO converter, where a copper promoted
iron/chromium- based catalyst is installed. The inlet temperature is 360C
and of the reaction takes place here, causing a temperature rise of 73C.
The second step is taking place in two converters, the LT guard vessel and
the secondary CO converter. Between the converters the process gas is
cooled in 2nd HHP BPW pre heater.

4.5.1 Primary CO Converter

34

The process gas outlet of the secondary reformer is cooled to 360C

in the reformed gas waste heat boiler and the 3 rd HHP BFW preheater
before entering the primary CO converter. The primary CO converter
contains 39.8 m3, 6 6 mm rings of the catalyst. SK-201 is a copper
promoted iron oxide catalyst and in the fresh catalyst the iron oxide is at
its highest oxidized level and is thus not affected by air, steam, carbon
dioxide or nitrogen at elevated temperatures. Normal operating
temperature for SK 201 is from 330C to 450C.
At the start up of the plant the catalyst must be activated, which is
mainly a reduction of Fe2O2 to Fe3O4. The reduction will take place
simultaneously with start- up of the reformer. When new, the catalyst can
operate at a gas inlet temperature of 360C. Afterwards the optimum inlet
temperature will be higher, but as the outlet temperature has not reached
450C, the activity will only decrease slowly. The cold catalyst can be
heated by steam alone, both when oxidized and reduced states. 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 steam.
Chlorine concentration of less than 10 ppm by volume in the feed gas will
have no effect on the catalyst activity. The catalyst is not influenced by
sulphur in the quantities present in the plant. The fresh catalyst contain,
however, less than 100 wt. ppm sulphur which will be given off as H 2S
during the first few days of operation before the LT shift converters are
put on line.
35

4.5.2 LT Shift Converters

The gas outlet is cooled to 210C in the converted gas waste heat
boiler producing 45 kg/cm2 g steam and in the primary medium pressure
boiler producing 11 kg/cm2 g steam. The CO conversion at low
temperature takes place in two reactors, the LT guard vessel and the
secondary CO converter. The LT guard vessel contains 47.2 m 3, 4.3
3.2mm rings of the Topsoe LK-821 catalyst containing of oxides of
copper, zinc and aluminium in two beds. On the top of the LK-821 a layer
of 2.6 m3, 4.5 4.5mm rings of Topsoe LSK catalyst is placed as a
chlorine guard. The LSK catalyst will also protect the main catalyst bed
against droplets of condensing steam.
The gas outlet is cooled to 190C in the 2nd HHP BFW preheater
before entering the secondary CO converter. It contains 51.2 m 3, 4.3 x
3.2mm rings of the Topsoe LK-821 catalyst. As the catalyst is extremely
sensitive to chlorine and sulphur which may be liberated not only from the
above mentioned HT shift catalyst, but to a certain extent also from the
refractory in the secondary reformer, the first period of operation are
bypassed during this stage until the gas is practically free of chlorine as
well as sulphur. The chlorine will normally be present in process steam,
quench water and process air in very small amounts. Besides chlorides,
sulphur and gaseous Si compounds are also poisons. When the catalyst is
in reduced state, temperature above 250C must normally be avoided

36

unless the catalyst is old. The normal operating temperature is between

190 - 275C.
A short exposure to 350C will have no adverse effect on the
catalyst. Normal operation should take place at as low a temperature as
possible. However, at temperatures near the dew point, the activity will
decrease because of capillary condensation of water inside catalyst pores,
thus reducing the free area. During operation the temperature should
maintained at a temperature atleast 20C above the dew point.
4.6 CO2 Removal
The gas leaving the separator unit has a CO 2 content of about 21%
by volume (dry basis). The gas enters the CO2 absorber at a temperature of
about 75C.
The CO2 is removed from the gas by absorption in a MDEA
solution containing 35 wt% MDEA. The MDEA solution also contains
3% Piperazine as activator. Piperazine increases the mass transfer rate of
CO2 from the gas phase to the liquid phase, the balance solution in water.
The overall reactions occurring during the CO2 absorption are described in
the following equations:
R3N + H2O + CO2 R3NH+ + HCO3- + Q

(1)

2R2NH + CO2 R2NH2+ + R2N-COO- + Q (2)

Reaction (1) describes the reaction for a tertiary amine (e.g.
MDEA). Reaction (2) describes the reaction for a secondary amine (e.g.
37

piperazine). In the CO2 absorber the CO2 is removed from the gas by
counter current absorption in two stages. In the lower part (bulk absorber)
of the absorber, flash- regenerated (semi-lean) solution is used for CO 2
removal. In the upper part stripper regenerated (lean) solution is used for
final CO2 removal. At the outlet of the absorber the CO 2 content in the gas
has been reduced to less than 500 vol. ppm on the dry basis. The solution
which enters the absorber at 50C (stripped solution) and 75C (flash
solution) is heated to 85C by the exothermic absorption reactions.
High interfacial areas between gas and liquid are provided by
2 CS, IMTP (Intaloz Metal Tower Packing) or cascade mini rings loaded
in 2 beds in the bulk absorber and by 1 CS IMTP or cascade mini rings
loaded in 3 beds lean absorber, respectively. To prevent losses of
scrubbing solution by entrainment in the purified gas, the top of the
column is provided with 3 bubble cap trays which are fed with
approximately 900-1300 kg/hr boiler feed water. The energy in the rich
solution leaving the bottom of the absorber is utilized in a hydraulic
turbine, which together with the steam turbine servers as driver for the
flashed solution main pump, thereby reducing the total steam consumption
of the process. The flash regeneration of the rich solution is performed in
two stages. In the HP flash drum the main part of the dissolved inert
components are liberated at a pressure of 6.2 kg/cm2 g. The flash gas is
used in the secondary HDS preheater. The LP flash drum is equipped with
the packing, 2 SS and CS pall rings and 2 bubble cap trays in the top.
38

The CO2 released in the LP flash drum is saturated with water at a

temperature of 75C. The mixture is cooled to 45.5C in the flash gas
cooler and the condensate is separated in the Knockout drum. The
condensate is returned to the regeneration system. The flashed solution
from the bottom of the LP flash is divided into two streams.
The major part of the solution is transferred to the lower part of the
absorber by means of the flash solution split steam pump. The rest of the
flashed solution before entering the top of the stripper is preheated in the
solution heat exchanger by means of lean solution coming from the
bottom of the stripper. In the CO 2 loading is achieved by using 2 SS pall
rings as packing material in two beds.
The CO2 leaving the top of the CO2 stripper at 98C is saturated
with water. This vapour is passed though the LP flash drum packed with a
1000 mm top layer of 2 SS and the bulk CS pall rings in one bed. The
lean solution from the bottom of the CO 2 stripper is cooled in the solution
heat exchanger, in the DMW preheater and in the lean solution cooler
before it is sent to the top of the CO 2 absorber by means of the lean
solution pump.

4.7 Methanation

39

After CO2 removal unit remaining trace amounts of CO and CO2

must be removed since these compounds are poisonous to the synthesis
converter. CO + CO2 are removed in the methanator vessel containing
nickel catalyst at the temperature of 320C. The reactions involved are;
CO2 + 4H2 CH4 + 2H2O + heat
CO + 3H2 CH4 + H2O + heat
Determining parameters for methanation reactions besides the
activity of the catalyst include temperature, pressure and the steam content
of the process gas. Low temperature, high pressure and low steam content
tend to favour the conversion of CO and CO2 into methane. However,
within the allowable temperature range, the equilibrium conditions are so
favourable that practically only the catalyst activity determines efficiency
of methanation. The higher the temperature, better the efficiency, but at
the same time it means a shorter life of the catalyst. Furthermore, in case
of a possible breakthrough CO2 or CO to the methanator, which would
result in a high temperature rise, a low inlet temperature is to be preferred
as this limits the temperature rise, low temperature is to be preferred as
this limits the temperature rise somewhat in connection with the lower
activity. The methanator gas normally contains less than 10 ppm CO and
CO2. The temperature rise will normally be about 2-5C.
The methanator is provided with one catalyst bed loaded with
17.18m3 of 6mm rings of the nickel catalyst supported on an alumina
40

base. As the reaction takes place at much lower temperature than those
prevailing in the reformers, the catalyst must be very active at lower
temperatures, whereas the performance of the catalyst at higher temp is of
minor interest.
Catalyst is very sensitive to sulphur, arsenic and chlorine
compounds. Steam without hydrogen will oxidize the catalyst and should
therefore not be used in heating, cooling or pursuing. Furthermore, it
should not be exposed to condensing steam as it will disintegrate the
catalyst. It is activated simply by heating it up with gas it should normally
treat. The content of CO and CO2 in the gas used for activation should be
as low as possible preferably close to specific gas.
The adiabatic temperature rise is about 75C per mole % CO and
60C per mole % CO2. The methanation reaction starts at a temperature of
about 240C, but in order to ensure a high reaction rate and a sufficiently
low content of CO and CO2 in the effluent gas, the operating temperature
would be from 290C to 350C , depending on the catalyst activity and the
gas composition . The methanator catalyst should not be exposed to
catalyst temperature above 450C for long periods of time.

4.8 Ammonia synthesis section

41

The ammonia synthesis in two ammonia converters, 1st NH3

synthesis converter and 2nd NH3 synthesis converter, according to the
following reaction formula;
3H2+ N2 2NH3 + heat
i.e. 3 volume of hydrogen plus 1 volume of nitrogen gives 2 volume of
ammonia
The reaction is an equilibrium reaction and therefore only part of
the hydrogen and nitrogen will be converted into ammonia by passing
through the catalyst beds. The composition of gas at chemical equilibrium
is influenced by pressure and temperature. High pressure and low
temperature tend to favour the reaction.
However .the reaction velocity is very much enhanced by high
temperature operation. Therefore, there is a compromise between the
theoretical conversion and the approach to the equilibrium in a single pass
over the catalyst. This relationship has the result that there is an optimum
level for the catalyst temperature at which the maximum production is
obtained. At higher temperature the equilibrium percentage (which is the
theoretical highest obtainable percentage of ammonia) will be lower,
while at lower temperature the reaction rate will be slower. The synthesis
unit is designed for a maximum pressure of 240 kg/cm 2 g, and the normal
operating pressure is about 200 kg/cm 2 g. The normal operating

42

temperature in the catalyst bed in H 170 is within the range 395-505C

and in H 1702 from 375C to 440C
Considerable amount of heat is liberated by the reaction (about 750
KCal/Kg produced ammonia) and a major part of the heat is utilized for
production of HP steam and preheating of HP boiler feed water.
According to the fact that in an equilibrium reaction only partial
conversion can be obtained, it is necessary to recycle the unconverted
synthesis gas to the converters. Approximately 33% hydrogen and
nitrogen contained in the synthesis gas at the first converter inlet is
converted in to ammonia per pass. In addition to the converter the
synthesis loop includes a recirculation compressor (integrated with syn
gas compressor) as well as equipment for steam production, boiler feed
water preheating, for cooling and condensation of the synthesis gas as
well as separation of the condensed ammonia.
The converter effluent gas is cooled in a number of steps, first in
the loop boiler from exit temperature of about 402C to 280C. Then in the
2nd HP BFW preheater to 193C, followed by the feed gas preheater and
the water cooler to about 38C, and finally in the cold exchanger and NH 3
cold exchanger to 1C. The condensed ammonia is separated from the
circulating synthesis gas in two separators and the secondary separator.
Make-up gas is introduced between exchangers. This make-up point has
been selected in order to remove any moisture and CO 2 in the make-up
43

gas, as water and CO2 gets dissolved in the liquid ammonia. When
entering the ammonia loop, the make-up synthesis gas is saturated with
water vapour and contains traces of carbon monoxide and carbon dioxide
(leakage from methanator). The water vapour concentration in the makeup gas is in the range 400-450 ppm, depending on the operating pressure
of the loop. The water is removed by absorption in the condensed
ammonia. Any tracer of carbon dioxide in the make-up gas reacts both
with gaseous and liquid ammonia, forming ammonia carbamate
NH3 + CO2 NH2-COO-NH4
The formed carbamate is dissolved in the condensed ammonia. The
carbon monoxide is only slightly soluble in ammonia and will pass with
reticulating gas to the ammonia converter where it is hydrogenated to
water and methane (methanation). As water deactivates the ammonia
synthesis catalyst, the carbon monoxide in the makeup synthesis gas
should be kept as low as possible.
The converters are radical type converters with gas flowing though
the catalyst beds in radical direction. S-200 converter, contains two
catalyst beds, an inter bed heat exchanger and a feed effluent heat
exchanger in the bottom. The converter contains Topsoe type KMIR
catalyst. The nominal diameters of the catalyst granules are 1.5mm to
3mm. Catalytic activity of the small particles are very high and the special

44

advantage of the radical converter is to allow the use of small particles

without a prohibitive pressure drop.
4.9 Refrigeration
The multistage flash drum consists of five compartments operating
at different pressures varying from 0.05 to 8.7 kg/cm2 and refrigeration
compressor forms the major part of the system. The vapours flashed at the
flash drum are sent to a refrigeration compressor. The compressor
compresses the vapours to 15.2 kg/cm2 pressure and discharge is sent to
ammonia condenser.
Condensed ammonia is separated in NH3 receiver and sent to
multistage flash drum. The inerts from the refrigeration system is mixed
with purge gas from synthesis section and is used as fuel in primary
reformer.

45

5. CO2 REMOVAL SECTION

5.1. Introduction
Carbon dioxide is an undesirable constituent in the synthesis gas
because it poisons the ammonia synthesis catalysts. CO 2 content in the
synthesis gas therefore must be reduced to 5 - 10 ppm by volume. CO 2
absorption is carried out by selective absorption after the low temperature
shift conversion. The CO2 removal processes are based on the chemical
and physical absorption of CO2 in a solvent. There are number of
processes available to remove CO2 from the synthesis gas. Based on the
process used, the gas absorption can be classified as physical or chemical
absorption process.
Physical absorption processes generally uses an organic solvent
which absorbs CO2 as a function of its partial pressure. Due to high CO 2
loadings, which are attainable, low circulation rates and less utility costs
are involved for these types of processes. The most commonly used
physical absorption processes is selexol process where solvent used is a
homologue of Di-Ethyl Ether of polyethylene glycols.
The chemical absorption process can be classified into three main
categories; the hot potassium carbonate process, the alkanolamines
process and other chemical absorption process. Commercially available
hot potassium carbonate processes are Benfield process, Glycine
Vetrocoke process and cataract process. In alkanol amines processes, the
46

solution has an amine component. Mostly used solutions were MonoEthanol Amine (MEA), Di-Ethanol Amine (DEA), etc. Present day most
preferred solution in alkanol amines processes is activated Methyl DiEthanol amine (a-MDEA).
Activated MDEA process for CO2 removal is a physical/chemical
absorption process. It behaves as a physical absorption process at higher
partial pressure of CO2 and as a chemical absorption process at low CO2
partial process. The bulk of the solution can be regenerated by simply
flashing, leading to very low energy consumption.
5.2. Various CO2 Removal Processes
CO2 removal is a significant step in ammonia production process
with respect to investment and energy consumption and due to fast
increasing energy cost, the CO2 removal processes are being continuously
improved. As a result of this the requirement of energy has been reduced
from 36000 Kcal/kmole of CO2 removed to about 9500 Kcal/kmole of
CO2 removed. CO2 can be removed by scrubbing the gas under pressure
with various solvents.
5.3 Solvents Used for CO2 Removal by Absorption
Following the shift conversion of CO with steam to oxygen and
hydrogen, the CO must be removed from the hydrogen and nitrogen.

47

Carbon dioxide can be removed by scrubbing the gas under pressure with
various solvents. Processes for CO2 removal include;
1. Hot Potassium Carbonate Benfield Process or Catacard
2. Water
3. Methyl Di-Ethanol Amine
4. Sulfinal Sulfolane
5. Fluro solvent propylene carbonate
6. Rectisol refrigerated methanol
7. Vetrocoke (arsenical)
8. Tri-Ethanol Amine
9. Selexol Di-Methyl Ether of polyethylene glycon
10. Alkaline potassium N-methyl amine propionate
11. Purison N-methyl pyrrolidone
Water Scrubbing:
This steam was used widely, has not remained competitive. A large
quantity of water is required to dissolve the carbon dioxide and special
design is needed to avoid excessive loss of nitrogen and hydrogen. Power

48

recovery is important and is achieved by use of properly designed

turbines.
Hot Potassium Carbonate:
In this system, an aqueous solution containing 40 % K2CO3 is recirculated at 118C in the absorber. The CO2 is picked up and released in
the stripper at atmospheric pressure by heating the solution of 230C. An
inhibitor is generally needed to reduce corrosion. Stainless steel
equipment is used in many places. This system is characterized by low
steam requirements and its compatibility with the catalyst. The system
may be modified by adding the materials that enhance the solubility of
CO2 and hence result in more complete recovery. Alkanol amine and AsO
are typical additives.
Methyl Di-Ethanol Amine (MDEA):
A 15 35% solution of MDEA in water is used to absorb the CO 2
under pressure. The solution then is generated by heating in a stripper in
which carbon dioxide is released. This system is characterized by good
absorption properties at high pressure. A corrosion inhibitor is used with
this process. With the amine guard inhibitor, the MDEA concentration in a
circulating solution can be increased to 30% from the normal 20%. Hence
the circulation rate decreases by 33% and heat requirements decrease to
43%. Stainless steel is used in critical areas, where hot carbon dioxide

49

laden solution is present. It is reported that anti-foam agents are used in

some cases with this process
Sulfinol Proceses:
The sulfinol process is a development by the Shell development
crop, in Emeryville, California. The solution consists of sulphonate, which
are a ring compound, di-isopropanol amine and water. This process is
characterized by its high CO2 retention under pressure and by low steam
requirements for regeneration. Side stream regenerators are required to
remove by-products that build up in the steam. Mild steel is suitable in a
manner of places, however stainless is preferred where CO 2 concentration
are high.
The process must be carefully engineered to protect the downstream
nickel catalyst from sulphur, which may be carried over from the absorber.
Likewise the CO2 that is produced must be protected from the entrainment
of the solvent and contamination with sulphur.

50

Salient features of different CO2 removal are given in table-5.1

Straight Solution

Single Stage

100

500

300

100

100

100

500

16,000

32,000

29,000

9,500

6,000

Selexol

Vetrocoke Glycine

100

Double Stage

Benfield

99.95

MEA UOP-IV

99.5

MEA UOP-II

99.4

19,000

99.0 99.0 98.5

25,000

CO2 Purity

36,000

Parameters

a- MDEA

99.95 98.5

CO2 slip in
product gas,
ppm
Energy
required

Table 5.1: Salient Feature of different CO2 removal systems

5.4. Advantages of Activated MDEA Process:

The main advantages of activated MDEA (a-MDEA) process as
against other processes are summarized below:

51

1. Higher CO2 removal in activated MDEA process with same

equipments and lower circulation rate.
2. Low inerts make-up in synthesis gas due to low CO 2 slip. This
was desired because the existing synthesis section is designed for low
inerts. Low CO2 slips with the product gas has further advantages such as
less consumption of H2 in the methanator, higher conversion per pass in
synthesis converter due to less inert and reduction in purge gas from
synthesis loop.
3. Purity of CO2 in case of activated MDEA processes is 99.8%
while in case of other process, it is about 98.5%. The hydrogen content in
CO2 in case of activated MDEA is less. The hydrogen content in CO 2
makes explosion mixture in urea plant and higher hydrogen increases the
ammonia losses. Higher hydrogen also has an influence on corrosion in
urea process because it contributes to hydrogen penetration and
consequent destruction of oxide film.
4. Utilisation of all the existing equipments i.e. not making any
changes in the system.

5. Low energy consumption

6. Lower MDEA make-up consumption

52

7. MDEA (Methyl Di-Ethanol Amine) is environment friendly and

bio-degradable chemical.
8. MEA solution is a corrosive solution, while MDEA is noncorrosive. Hence MDEA system does not require any corrosion inhibitor.
5.5 Consideration of Operation Parameters
The operating parameters for each application should be carefully
examined. For the case of bulk CO2 removal using MDEA and mixtures of
amines, the most sensitive operating parameters include:

Liquid Residence Time on Tray:

Since the CO2 reaction rate with MDEA is slow, the column
diameter and weir height must be adjusted to give sufficient time for the
reaction to occur. The usual range of weir heights are from 2" - 4"
resulting in residence times from about 2 - 5 sec.
Lean Amine Temperature:
Usually the only parameter available for control of the column
temperature is the lean amine temperature. Since the CO 2 reaction with
MDEA is kinetically controlled, the hotter the column the faster the
reaction rate. However, once the lean amine temperature reaches about
135-140F, the decrease in solubility of CO 2 in the amine solution will
53

usually become the overriding factor and the net CO 2 pickup will begin to
decrease.
Circulation Rate:
As is the case for primary and secondary amines, when the
circulation rate is increased for any given column, the CO 2 pickup will
increase. This usually holds true for MDEA in a column of fixed diameter
even though the liquid residence time on a tray will decrease with
increased circulation.
Steam Stripping Rate:
For any given situation, as the steam stripping rate is increased, a
leaner amine will be produced which will result in a higher CO2 pickup.

54

CO2 Gas
CO2 Stripper

Semi-Lean Solution
Purified Process Gas

LP Flash Drum

Rich CO2 Gas

Lean Solution

Boiler Feed Water

CO2 Absorber
Semi-Lean Solution

HP Flash Drum

Heat Exchanger

Process Gas

Lean Solution

Figure 5.1 CO2 Removal Section (MDEA Section)

55

6 MATERIAL BALANCE
6.1 Overall Material Balance
Ammonia Production

1050 MT/Day

43759 Kg/hr

Molecular Weight

17.0306 Kg/Kmole

Moles of ammonia Produced

43759/17.0306

2568.905 Kmole/hr

3 moles of H2 react with 1 mole of N2 to form 2 moles of NH3

3H2 + N2 2NH3
Hence of 2568.905 moles of NH3,
Moles of H2 required

2568.9053/2

3853.358 Kmole/hr

Naphtha required per day

536.544 Ton

Moles of N2 required

2568.905/2

1284.453 Kmole/hr

Air Required ( as N2 supply)

36890.90 Nm3/hr (data)

Steam Required

93687 Kg/hr

56

(data)

(data)

6.2 Material Balance of CO2 Absorber

Purified Gas
Flow Rate = 127994 Nm3/hr

Boiler Feed Water

Lean Solution

Flow Rate = 0.794 ton/hr

Flow Rate = 269.6 ton/hr

Semi Lean Solution

Flow Rate = 1712.219 ton/hr

Process Gas
Flow Rate = 164714 Nm3/hr

Liquid Outlet
Flow Rate = 2168.8 ton/hr

57

Inlets:
Streams

Kg/hr

Process Gas

Nm3/hr

Ton/hr

164714

335.734

Semi-Lean Solution

1712219

1712.219

Lean Solution

269600

269.6

Boiler Feed Water

794

0.794

Total flow rate

Density of process Gas

2318.347

(259000 101325) 16.1894

346 8314.51
=

= 2.03828537 kg/m3
Process Gas flow rate

= 164714 Nm3/hr
= ( 164714 2.0382837 ) kg/hr
= 335734.1364 kg/hr
= 335.734 ton/hr

58

Process Gas Components

Component

Mol. Wt (MWi)

Nm3/hr

moles/hr

Mole Fraction ( xi )

xi*MWi

Hydrogen

95432

4257.6961

0.5794

1.1588

Nitrogen

28

31625

1410.9485

0.1920

5.3760

Carbon Monoxide

28

64

2.8554

0.0004

0.0109

Carbon Dioxide

44

34780

1551.7088

0.2112

9.2908

39.94

381

16.9983

0.0023

0.0924

Methane

16

426

19.0060

0.0026

0.0414

Water

18

2006

89.4976

0.0122

0.2192

164714

7348.7106

1.0000

16.1894

Argon

59

Outlets:
Streams
Purified Gas
Liquid Outlet

Nm3/hr

Tons/hr

127994

149.547

Kg/hr

2168800

2168.8

Total

2318.347

(257000 101325) 8.6749

323 8314.51
Density of Purified Gas =

= 1.152831656 kg/m3
Purified gas flow rate

= 127994 Nm3/hr
= ( 127994 1.152831656 )
= 149547.1364 kg/hr
= 149.547 tons/hr

60

Purified Gas Components

Component

Mol. Wt (MWi)

Nm3/hr

moles/hr

Mole Frac ( xi )

xi*MWi

Hydrogen

94921

4234.897832

0.7416

1.48321015

Nitrogen

28

31539

1407.111627

0.2464

6.899479663

Carbon Monoxide

28

64

2.855358258

0.0005

0.014000656

Carbon Dioxide

44

64

2.855358258

0.0005

0.022001031

39.94

380

16.95368966

0.0030

0.118577433

Methane

16

424

18.91674846

0.0033

0.053002484

Water

18

602

26.85821362

0.0047

0.084660218

127994

5710.448827

1.0000

8.674931637

Argon

61

6.3 Material Balance of CO2 STRIPPER

CO2 Rich Gas

Flow Rate = 17697 Nm3/hr

Semi Lean Solution

Flow Rate = 292300 kg/hr

Lean Solution
Flow Rate = 269600 kg/hr

Inlets:
62

Streams

Kg/hr

Semi Lean Solution

292300

Nm3/hr

Ton/hr
292.300

Total Outlet flow rate

292.300

Outlets:
Streams

Kg/hr

Lean Solution

269600

CO2 Rich Gas

22685

Nm3/hr

269.600
17697

Total Outlet flow rate

22.685
292.285

CO2 Rich Gas flow rate = 17697 Nm3/hr

17697 28.732
22.414
=

= 22685.384 kg/hr
= 22.685 ton/hr

6.4 Material Balance of Heat Exchanger

Hot Fluid
Inlet Gas Flow Rate

Ton/hr

195463 Nm3/hr
63

1.8811 Kg/m3

Density of Inlet Gas

Inlet Mass Flow Rate

(195463 1.8811)

368025.758 Kg/hr

368.026 Ton/hr

175332 Kg/hr

175.332 Ton/hr

Cold Fluid
Inlet Liquid Flow Rate

7. ENERGY BALANCE
7.1. Energy Balance of Heat Exchanger
Cold Fluid (Water) Details
Flow Rate

175332 Kg/hr
64

Inlet Temperature

40C

Outlet Temperature

80C

J
4185 Kg.K

Specific Heat

Hot Fluid (Process Gas) Details

Flow Rate

368025.758 Kg/hr

Inlet Temperature

127C

Outlet Temperature

93C

J
2345.63 Kg.K

Specific Heat

m C

T h

=
=

m C

T c

=
=

(36802758 2345.63 ( 12793 ) )

29350.577 MJ/hr
(175332 4185 ( 8040 ))

29350.577 MJ/hr

8. EQUIPMENT DESIGN
8.1 Design of CO2 Absorber
Design of Bottom Section ( Bulk Absorber )

65

Liquid Flow Rate

Flow

Rate

of

Lean

Solution

Flow Rate of Semi-Lean Solution +

Flow Rate of Boiler Feed Water(BFW)
=

269600 + 1712219 + 794

1982613 kg/hr

Flow Rate of Process Gas

137897.7812 kg/hr

Density of MDEA

1070 kg/m3

Inlet Pressure of gas

25.9 kg/cm2 g

(259000+101325) kg/m2 (or) Pa

(259000 101325) 16.1894

346 8314.51

2.03828537 kg/m3

25.7 kg/cm2 g

(257000+101325) kg/m2 (or) Pa

(257000 101325) 8.6749

323 8314.51

1.152831656 kg/m3

1.595558513 kg/m3

Gas Flow Rate

Density of Inlet Gas

Outlet Pressure of gas

Density of Outlet Gas

Average Density ()

66

L
G

g
l

1982613
( 137897.7812
) 1.595558513
1070

14.37741045 0.00149117618

From the value of

L
G

g
l

0.555194493

, from the correleations of system physical

properties and packing properties, we get

K4

0.52

From this value of K4, the mass velocity per unit square meter can be
calculated used the relation given below,

13.1 V Fp L
L
v ( L v )

0.1

* 2
w

K4

13.1F p L / L

Vw*

0.52 1.59555 1070 1.59555

0.1
13.1 59 0.001 / 1070

Vw*

2.144042635 Kg/m2.s

Vw*

1/ 2

K 4 v L v

Mass Velocity / m ,

67

0.1

1/ 2

Figure 8.1 Generalised pressure drop correlation for IMTP Packing

Column Area Required

Column Area Required

Column Diameter , D

Gas mass flow rate/Mass velocity per m2

137897.7812/3600
2.144042635

17.86575444 m2

4 17.86575444
3.1416
68

4.768462431 m

NTU Calculation
X1 = ?

Y1 =

0.214901

X2 = 0.025

Y2 =

0.0257

Inlet gas flow rate

MDEA solution flow rate=

L
G

36498.748
20490.18 =

20490.18 kmol/hr
36498.74816 kmol/hr
Y1 Y2
X1 X 2

0.214901 0.0257
X 1 0.025

X1

0.131216315

0.8x

X
0.8 1 X

Y
1 Y

69

When X1 = 0.131216315,
Y1e
1 Y1e =

Y1e

0.131216315
0.8 1 0.131216315

0.102288664

Y2 e
1 Y2 e =

0.025
0.8 1 0.025

When X2 = 0.025,

Y2e

0.019900498

Y1 Y2

NTU =

Y1 Y1e Y2 Y2e / ln

Y1 Y1e
Y2 Y2e

0.214901 0.257

NTU

0.214901 0.1023 0.257 0.0199 / ln 0.214901 0.1023

0.257 0.0199
=

NTU =

5.254088288

HTU Calculation

HTU =

Q
K ga P

20490.18 120.801 (346-323)

56929895.86 Kg/m2.hr.Pa
70

Kga

25.9 kg/cm2 g

(259000+101325) kg/m2 (or) Pa

360325 Pa

32.87 Kg/m3.hr.Pa

HTU =
=

56929895.86
32.87 3603325

4.8067 m

Height of Bottom section of Absorber =

Hb

NTU HTU

5.254088288 4.8067

25.25478 m

Design of Top Section

Liquid Flow Rate

Flow

Rate

of

Lean

Solution

Flow Rate of Boiler Feed Water(BFW)

Gas Flow Rate

269600 + 794

270394 kg/hr

Flow Rate of Process Gas

58958.19635 kg/hr
71

Density of MDEA

1070 kg/m3

Inlet Pressure of gas

25.9 kg/cm2 g

(259000+101325) kg/m2 (or) Pa

(259000 101325) 16.1894

346 8314.51

2.03828537 kg/m3

25.7 kg/cm2 g

(257000+101325) kg/m2 (or) Pa

(257000 101325) 8.6749

323 8314.51

1.152831656 kg/m3

1.595558513 kg/m3

Density of Inlet Gas

Outlet Pressure of gas

Density of Outlet Gas

Average Density ()
L
G

g
l

270394
58958.19635

1.595558513
1070

4.586198641 0.00149117618

0.177099502

72

From the value of

L
G

g
l

, from the correleations of system physical

properties and packing properties, we get

K4

1.3

From this value of K4, the mass velocity per unit square meter can be
calculated used the relation given below,

13.1 V Fp L
L
v ( L v )

0.1

* 2
w

K4

*
w

Vw*

1/ 2

K 4 v L v

13.1F p L / L

0.52 1.59555 1070 1.59555

0.1
13.1 134 0.001 / 1070

0.1

1/ 2

*
Mass Velocity / m2, Vw =

2.249453542 Kg/m2.s

Column Area Required

Gas mass flow rate/Mass velocity per m2

58958.19635/3600
2.249453542

7.280557903 m2

Column Area Required

73

Column Diameter ,D

4 7.280557903
3.1416

3.044037619 m

NTU Calculation
X1 = ?

Y1 =

0.0257

X2 = 0

Y2 =

0.0005

Inlet gas flow rate

3760.51 kmol/hr

MDEA solution flow rate=

5816.08 kmol/hr

Y1 Y2
X1 X 2

5816.08
3760.51

0.0257 - 0.0005
X1

X1

0.016293595

0.8x

X
0.8 1 X

L
G

Y
1 Y

When X1 = 0.016293595,
Y1e
1 Y1e =

Y1e

0.016293595
0.8 1 0.016293595

0.012992537
74

When X2 = 0,
Y2 e
1 Y2 e =

Y2e

0
0.8 1 0

Y1 Y2

NTU =

Y1 Y1e Y2 Y2e / ln

Y1 Y1e
Y2 Y2e

0.0257 0.0005

NTU =

0.0257 0.013 0.0005 0 / ln 0.0257 0.013

0.0005 0

NTU =

6.678740962

HTU Calculation

HTU =

Q
K ga P

8760.5 120.801 (346-323)

24340376.98 Kg/m2.hr.Pa

25.7 kg/cm2 g

(257000+101325) kg/m2 (or) Pa

358325 Pa

75

Kga

HTU =
=

21.38 Kg/m3.hr.Pa
24340376.98
21.38 358325

3.1772 m

Height of Top section of Absorber

Ht
Total Height of Absorber

NTU HTU

6.678740962 3.1772

21.21959 m

Hb + Ht

25.25478 + 21.21959

46.4744 m

76

Design Summary:
The Absorption Column for the absorption of CO2 using the MDEA
solvent was designed and the following design details were found,
Bottom Absorber Diameter

4.768462 m

Bottom Absorber Height

25.25478 m

Top Absorber Diameter

3.04404 m

Top Absorber Height

21.21959 m

Total Height

46.47440 m

77

8.2 Design of a CO2 Stripper

Inlet fluid flow rate

= 292300 kg/hr

Outlet flow rate of liquid

= 269600 kg/hr

Outlet CO2 rich gas

= 22700 kg/hr

Composition of Inlet fluid :

Component

Formula

Mole %

Mole/hr

Kg/hr

Carbon Di-Oxide

CO2

5.58

276.91

12183.91

C5H13NO2

37

1836.12

218682.05

Piperazine

C4H10N2

148.87

12823.47

Water

H2O

54.42

2700.59

48610.57

Methyl Di-Ethanol
Amine

Inlet Fluid Temperature Tin

= 98 C
= 371 K

Pressure

= 1.39 atm.
= 140841.75 Pa

Composition of Outlet fluid :

Component

Formula

Mole %

Mole/hr

Kg/hr

Carbon Di-Oxide

CO2

0.47

18.99

835.76

78

Methyl Di-Ethanol

C5H13NO2

45.07

1836.12

218682.05

Piperazine

C4H10N2

3.65

148.87

12823.47

Water

H2O

50.81

2069.93

37258.72

Amine

Outlet Fluid Temperature Tout

= 113 C
= 386 K

Inlet CO2 flow rate

= 12183.91 Kg/hr

Outlet CO2 flow rate

= 835.76 Kg/hr

CO2 Stripped from Inlet stream

= 12183.91 835.76
= 11348.15 Kg/hr

Diameter of the column:

G
D = 1.128 G'

0.5

( )

Where,
G

= mass flow rate of gas

79

= 22700/3600
= 6.3056 Kg/sec
G

= mass flux of gas

To find G, first the flow parameter X is to be found

L

= Mass flow rate of liquid stream

= 269600/3600
= 74.89 Kg/sec

= Density of Gas
=

140841.75 25.5466
8314.51369.15

Kg/m3

= 1.172264689 Kg/m3
l

= Density of Liquid
= 1035 Kg/m3

L
G

g
l

74.89 1.1723
= 6.3056 1035

= 0.3997
Value of gas mass flux G is got from General Pressure Drop Correlations
in Rule of Thumbs for Chemical Engineers 4 Ed ( Pg. No. 101,102 )
80

Figure 8.2 Generalized Pressure Drop Correlation

G

= 1.2197
6.3056
1.128
1.12197

= 2.57 m

0.5

Height Equivalent of Theoretical Plate (HETP):

HETP is calculated as
HETP=

0.19

0.21

[ ] [ ]

20

0.2

Where,
A = Size of packing = 90mm
81

 = Surface tension of the liquid = 30 mN/m

= Overall viscosity of the feed stream = 1.8375 104 m2 / s

HETP=
HETP=

90 10

3 0.19

30 10
20

] [

1.8375 10
0.2

4 0.21

0.07129 m

Number of Transfer Units (NTU)

NTU =

1
x y1
ln 1 2

1
x1 y1

Where,
x2

= Solute content in liquid inlet stream in mole fraction = 0.058

x1

= Solute content in liquid outlet stream in molefraction = .0047

y1

= Solute content in gas at bottom in mole fraction = 0

L
GH

= Henrys Constant

= Molar Liquid flow rate

= 4073.91 Kmole/hr
82

= 888.58 Kmole/hr

= 3.47 KPa / mole fraction

4073.91
3
= 888.58 3.47 10

= 0.001309926

1
0.00470
NTU = 10.00131 ln ( 10.00131 ) 0.05580 +0.00131

= 2.47625476
Height of Overall Gas Transfer Unit (HOG)

HOG

1
1

1
ln

= HETP

1
0.00131
1

ln

= 0.07129 0.00131

= 8.18592
Column Height
Total Height = HOG NTU
= 8.18592 2.47625476
83

= 20.123 m
Giving 0.45m allowance for disengegment of vapours at top and liquid at
bottom
Total Height = 21.023 m.
Design Summary:
The Stripper Column for the stripping of CO2 from MDEA solution was
designed. The following design details were found,
Diameter of the Stripping Column

2.57 m

Height of the Stripping Column

21.023 m

8.3 Design of Heat Exchanger

Specifications

Units

Fluid

Shell Side

Tube Side

Water

Process Gas

Inlet Temperature

40

127

Outlet Temperature

80

93

Specific Heat

KJ
Kg.K

4.185

2.345

84

Thermal Conductivity

W
m.K

0.65439

0.03419

Viscosity

Pa.s

4.664 104

1.599 105

Density

Kg
m3

983.2

1.8811

Fouling Coefficient

W
m 2 C

500

3500

Heat Duty of Heat Exchanger

Q

( mCpT )h

( 102.22942345.6334)

29350.5768106 J/hr

8152938 J/sec

To find LMTD
Tc1

40C

Tc2

80C

Th1

127C

Th2

93C

T1

53C

T2

47C

85

LMTD

T1 T2
T1

ln

T
2

49.939942C

53 47
53
ln

47

For 1 shell and 1 tube pass

LMTD Correction Factor

Corrected LMTD, TLMTD

49.939942C

86

To find number of tubes

Let us assume the overall heat transfer co-efficient,

Uo

W
2
300 m C

To find the area required,

Q

UoATLMTD

Q
U o TLMTD

8152938
300 49.9399

84.1142 m2

Assume,
Outer diameter of inner tubes

20 mm

Inner Diameter of inner tubes

16 mm

Length of tubes

4.83 m

Area of one tube

Do L

0.02 4.83

0.3036
87

No of tubes, NT

88.1142
0.3036

277 tubes

Film Co-Efficient of Film Side

hi Di
k =

0.023 Re

0.8

Pr

0.33

0.14

where,

Re

Reynolds Number =

DiV

Cp

Prandtl Number

Thermal Conductivity of process gas

W
0.03419 m.K

Specific Heat of process gas

KJ
2.34563 Kg.K

Viscosity of process gas

1.59910-5 Pa.s

Density of process gas

Kg
3
1.8811 m

Cp

Pr

88

Cross Sectional Area of one tube

Di 2
4

0.016 2
4

2.01143 10-4 m2

2.01143 10-4 277

5.5727 10-2 m2

Kg
2
6.6211853 m .s

Linear Velocity

m
3.51984012 s

Reynolds Number

18349.83

2345.63 1.599 10 5
0.03419

1.097

Total Flow Area

Mass Velocity

Prandtl Number

0.023 18349.83

hi

W
2
4744.67773 m C

89

1.0974
0.016

0.8

0.33

0.03419

Film Co-efficient of Shell Side

hi De
k =

j h Re Pr

1/ 3

where,

Re

Reynolds Number =

DiV

Cp

Prandtl Number

Thermal Conductivity of process gas

W
0.65439 m.K

Specific Heat of process gas

KJ
4.185 Kg.K

Viscosity of process gas

4.664 10-4 Pa.s

Density of process gas

Kg
3
983.2 m

Cp

Pr

90

Bundle Diameter
Here ki

Bundle Diameter

Shell Diameter

Tube Pitch

Baffle Spacing

Total Flow Area

=
=

0.249,

N
Do T
ki

2.207
1

277
0.020

0.249

0.48012 m

0.48012 + 0.068

0.54812 m

1.25 20

25 mm

0.54812
5

0.10962 m

2.207

2
Ds 2
N T Do
4
4
-

0.54812 2 277 0.02 2

4
4
-

0.148983 m2
91

Kg
2
326.9057 m .s

Linear Velocity

m
0.3325 s

Reynolds Number

9953.6621

4185 4.664 10 4
0.65439

2.98275

0.023

1. 1
2
pt2 0.917 d o
do

0.014201 m

hs De
k

j h Re Pr

hs

0.023 9953.6621 2.98275

0014201

W
2
1518.5680 m C

Mass Velocity

Prandtl Number

jh Factor

Equivalent dia, De

92

1/ 3

0.33

0.65439

Overall Heat Transfer Co-efficient

1
U

1
1

ho hod

1
1

= 1518.568 500

do
di

d o ln

2k w

do 1 do 1
d i hid d i hi

0.02

1
0.016 0.02 1 0.02
2 45
0.016 3500 0.016 4744.677

0.02 ln

W
2
300.4177 m C

Shell Side Pressure Drop

4f

L 2
v
D

Where,
f

dimensionless friction factor

Length of the Shell

Diameter

Density of fluid flowing in shell

Linear Velocity of the fluid flowing in shell

93

4 0.00396

416.27 Pa

0.416 kPa

4.83
983.2 0.3325 2
0.020

Tube Side Pressure Drop

L ut
8 jf
di 2

jf

dimensionless friction factor

Length of the tubes

di

Inner Diameter of the tubes

Density of fluid flowing in tube

Linear Velocity of the fluid flowing in tubes

Where,

94

From the Tube-side friction factor chart, the value of jf has been found to

be 0.04

4.83 1.8811 3.51984 2

8 0.04

0.020
2

900.525 Pa

0.9 kPa

Design Summary:
The Shell and Tube Heat Exchanger for the cooling of process gas was
designed and the following design details were found,
Design Specifications

Value

Inner Diameter of Tubes

16 mm

Outer Diameter of Tubes

20 mm

Length of Inner Tubes

4.83 m

No. of Tubes

277
95

Shell Diameter

0.54812 m

Bundle Diameter

0.4812 m

Overall Heat Transfer coefficient

W
2
300.4177 m C

Shell Side Pressure drop

0.418 kPa

Tube Side Pressure drop

0.900 kPa

9. SAFETY ASPECTS IN MFL

9.1. General Safety Aspects
Almost all the chemicals handled in this plant as a raw material,
intermediate or final products can cause injury to personnel if improperly
handled. The operators should be thoroughly acquainted with the
hazardous properties of all the chemicals handled and should be trained in
the proper ways to handle materials in order to reduce personal contact to
a minimum. The general overview for handling these materials and
protecting personnel are explained below.
The potentially hazardous materials in this plant are:
1. Ammonia
2. Liquid ammonia
96

3. Urea
4. Carbonate
5. Carbon dioxide in non-ventilated area.
9.2. Handling Hazardous Materials
In general it should be emphasized that operates should minimize all
physical contact with the chemicals handled in this plant by considering
the following rules:
1. Keep chemicals within closed containers at all times.
2. Utilize proper protective clothing and equipment if the chemicals
cannot be kept within closed containers.
9.3. Safety in Use of Pressurized Vessels
All vessels should be completely drained, depressurized, purged and
vented before opening and/or attending for inspection on maintenance.
From an environmental, atmospheric aspect, vessels should preferably be
drained to another vessel before opening. If this cannot the accomplished,
the next most desirable procedure is to drain vessels to drums. If drained,
full precaution should be taken to prevent sledge, atmospheric
contamination and excessive flashing in the sewers. Vessels should be
depressurized back to process if possible.

97

Once drained and depressurized, vessel entry procedures must be

followed. The minimum requirements consisting of oxygen and
combustible gas monitoring prior to vessel entry, disconnecting of all
piping to the vessel, lock out of motors, equipment vessel entry personnel
with safety harnesses and keeping fire watch and safety conservers on
hand while personnel are in the vessel and maintaining constant
communication with those inside.

9.4. Safety in Use of Tools and Steam Hoses

Powered tools, hand tools, should all be in good safe working
condition. Electric cables grounding should be intact. Ropes and pulleys,
slings should not be frayed. Ladders should be intact.
Be sure that all steam hoses are in good condition and that all
connections are made tight so that there is no chance of a leak that could
cases scalding of an operator. Hoses should also be tied down so that they
are accidentally disconnected by vibration or other outside agents that the
loose hose end does not whip about. Crack the steam valve at first until all
water in the hose is discharged and the hose is heated up, in order to
prevent high velocity jets of water from issuing from the hose.

98

Because compressed air cannot be seen, very few operators

appreciate the hazards when using it. Goggles should be worn when air is
used for cleaning of clothes as small particles of dirt can get into the skin.
When handling with steam hoses, precautions should be taken to ensure
good conditions, tight connections and tie-down hoses in case they
disconnect.
Repairing Leaks
Because of the hazardous nature of the chemicals handled in the
plant, leaks should be repaired immediately, whenever possible. Leaks in
the reactor feed or reactor effluent system must be repaired. Piping,
vessels, heat exchangers and other equipment should be thoroughly
drained, depressurized and purged before performing maintenance.
First Aid
All operators should be trained to recognize the hazardous effect of
the carious chemicals handled and to perform the necessary first air
procedure to minimize personnel injury.
The plant physician should be made acquainted with the carious
chemicals being handled so that he will be prepared to take the necessary
medical action without delay in the event of serious personnel exposure.
Goggles, Gloves, Masks, Etc.

99

At all times operators and other personnel within the plant should
be fully clothed with long trousers, long-sleeved shirts, hats, safety glasses
and safety shoes.
In order to decrease the possibility of hazardous contacts with
chemicals, operators should be compelled to wear suitable goggles where
applicable.
Small liquid anhydrous NH3 and Liquid ammonia leaks from drain
or vent valves or packing around valves can go unnoticed and can cause
eye injuries.

All operators should have a pair of work gloves to protect their

hands from contact with chemicals when they are performing operation on
the process equipments.
Since gas masks are of limited value for highter concentration of
gases, it is desirable to have available self contained air masks which will
be marked and easily available in the work area. Escape respirators should
be carried by all personnel in the operating areas.
Other conventional fire and safety equipment, such as fire blankets,
extinguishers, etc, should be readily available to all operating services and
maintenance personnel. The plant safety program should include training
and periodic refresher training of all personnel. In respect to safe use of
100

the safety and first aid equipment, response teams should be set up to
assist workers when they are in danger.

10. CONCLUSION:
In this project, a study of the manufacture of ammonia by Haldor
Topsoe Process was done. A detailed study was done on the MDEA
section where CO2 is absorbed from the process gas because CO2 acts as a
catalytic poison to the ammonia synthesis and Separation of CO 2 from
Synthesis gas using MDEA Absorber was done. Structural packing gives
the following advantages by increased capacity for exiting towers,
reduced CO2 content in product gas, and decreased reboiler heat duty,
greater mass transfer and hydraulic capabilities, twice the surface area per
unit volume and lower pressure drop.

101

11. BIBLIOGRAPHY
1. Robert E. Treybal, Mass Transfer Operations, 3rd Ed., McGraw-Hill
Book Company, 1981
2. McCabe W.L., Smith J.C. and Harriott P., "Unit operations of
Chemical Engineering", 7th Ed., McGraw-Hill, 2004
3. D. Q. Kern, Process Heat Transfer", Tata McGraw Hill Publishing
Co., New Delhi, 1990
4. Madras Fertilizers Plant Process Manual
5. R.K. Sinnott, Coulson & Richardsons Chemical Engineering Series
Volume 6, Chemical Engineering Design , 4th Edition, Elsevier
Butterworth-Heinemann, 2005
102

6. Don W. Green, Robert H. Perry, Perrys Chemical Engineers

Handbook, 8th Edition, McGraw-Hill Publishing Co., 2008
7. Carl Branan, Rules of Thumb for Chemical Engineers, 4th Edition,
Elsevier Butterworth-Heinemann, 2005
8. J.M. Coulson & J.F. Richardson, Coulson & Richardsons Chemical
Engineering Series Volume 1, Fluid Flow, Heat Transfer and Mass
Transfer, 6th Edition, Elsevier Butterworth-Heinemann, 1999

103