ACKNOWLEDGEMENT

I wish to express my sincere gratitude to Mr. Joseph Miranda (DGM,

Training) and Mr. S.N Srivastava (Manager,Training) for providing me an
opportunity to do my internship and project work at INDIAN FARMERS
FERTILISER COOPERATIVE LIMITED, Paradeep Unit.

I sincerely thank Mr. A.P Tripathi (Chief Manager, SAP) for the positive
attitude he showed for my work and constantly encouraging to complete the
same.

I would also like to acknowledge my heartfelt gratitude to Mr. S.K

Mondal, Mr. Ravitej Kumar ( GET ), and Mr. A.K Soni for spending their
valuable time with me and always allowing me to question them and giving
prompt replies for my uncertainties in all the fields associated with H2SO4
production.

I would also like to thanks Mr. K.C Barik (librarian) for providing the
necessary materials about SAP including the operating manual and other
valuable magazines .

Finally, it is always a pleasure to remind the fine people in the plant for
their sincere guidance I received to uphold my practical as well as
theoretical skills in engineering.

Shantanu Chatterjee

B.Ch.E, Jadavpur University

1|Page
 INDEX
CONTENT PAGE NO.
1. INTRODUCTION ……………………………………….03

2. OVERVIEW OF H2SO4

MANUFACTURING ……………………………………06

3. DETAILED PROCESS

DESCRIPTION

3.1 MELTING AREA …………………………………..10

3.2 SULPHUR COMBUSTION……………………….14

3.3 WASTE HEAT BOILER SYSTEM……………… 18

3.4 CONVERTER SYSTEM………………………… 24

3.5 DRYING AND ABSORPTION SECTION……….27

3.6 ALKALI SCRUBBING SECTION………………..35

4. FIRE AND SAFETY………………………………...…….37

5. ASSIGNMENTS………………………………………..…39

2|Page
1. INTRODUCTION
 1.1 About IFFCO :- Indian Farmers Fertiliser Cooperative
Limited, also known as IFFCO, is the world's
largest fertiliser cooperative federation based in India which is
registered as a Multistate Cooperative Society. IFFCO has 40,000
member cooperatives. IFFCO has been ranked#37 in top companies
in India in 2011 by Fortune India 500 list.
On 3 November 1967 Indian Farmers Fertiliser Cooperative Limited
(IFFCO) was registered as a Multi-unit Co-operative Society. It got
deemed recognition under the provisions of Multistate Cooperative
Societies Act 1984 & 2002 later.
During the year 2008–09 IFFCO produced 7,168,000 tonnes of
fertiliser material; registering overall capacity utilisation of 98 percent
for nitrogenous and 53 per cent for phosphate fertiliser. It contributes
21.4% of country's total nitrogenous fertiliser production and 27% of
total phosphate fertiliser production in the same period. Plant
productivity during the year stood at 1373 tonnes/person. The Society
has also achieved another important landmark in the field of energy
conservation by clocking overall annual energy of 5.943 Gcal/tonne of
urea. The Society has cloaked an all-time high sales of 11,258,000
tonnes of fertilizer during 2008–09.

Some of the diversifications and joint ventures are listed below –

 Indian Potash Limited in India

 Industries Chimiques du Senegal(ICS) in Senegal
 Oman India Fertiliser Company(OMIFCO) in Oman
 Indo Egyptian Fertiliser Company (IEFCO)
 Jordan India Fertiliser Company in Jordan
 IFFCO Tokyo General Insurance Company Limited (ITGI)
 Equity in National Commodity and Derivatives
Exchange (NCDEX) and National Collateral Management
Services Limited
 IFFCO Chhattisgarh Power Limited
 IFFCO Kisan Sanchar Limited(IKSL)
 KISAN Special Economic Zone (IKSEZ) at Nellore in Andhra
Pradesh
 In February 2010, it was announced that IFFCO had entered
into a joint venture partnership with GrowMax Agri Corp, a
subsidiary of Americas Petrogas Inc

3|Page
 1.2 Various Units of IFFCO :- IFFCO has five fertiliser
production units in India, which are situated in KALOL, KANDLA,
PHULPUR, AONLA and PARADEEP. Production capacities of the above
mentioned plants are listed below:-

KALOL: Ammonia-Urea complex commissioned in 1975

Ammonia: 0.36 MMTPA

Urea: 0.55 MMTPA

KANDLA: NPK/DAP complex commissioned in 1975

NPK/DAP: 2.42 MMTPA

In terms of P2O5: 0.910 MMTPA

PHULPUR: Ammonia-Urea complex commissioned in 1981

Ammonia: 0.824 MMTPA

Urea: 1.416 MMTPA

AONLA: Ammonia-Urea complex commissioned in 1988

Ammonia: 1.148 MMTPA

Urea: 2 MMTPA

PARADEEP: NPK/DAP, SAP, PAP plant acquired in 2005

NPK/DAP: 2 MMTPA
Sulphuric Acid: 2*3500 MTPD
Phosphoric Acid: 2650 MTPD

MMTPA- Million metric ton per annum

MTPD- Metric ton per day

4|Page
  1.3 IFFCO Paradeep Unit :- IFFCO Paradeep plant is spread
over an area of 2077 acres is an integrated phosphatic fertilizer
complex having world‟s largest phosphoric acid plant with two
streams of sulphuric acid and three granulation trains capable of
producing DAP, NP & NPK (grade-I and grade-II) fertiliser, bagging
plant, material handling facility, effluent treatment plant(ETP), sewage
treatment plant(STP), DM plant, a captive power plant and offsite
facilities to import raw materials /intermediates and to export
phosphoric acid. The unit is located just adjacent to the deepest
natural major port in India with 13 meters draft. IFFCO has its own
jetty for unloading imported raw materials.

The raw materials required by the complex i.e. Rock Phosphate,

Sulphur, Ammonia, Sulfuric Acid are shipped from the various
overseas ports and unloaded in the port. The annual requirement of
raw materials are as follows-

RAW QUANTITY/YEAR(Tons) SOURCES

MATERIALS
Rock Phosphate 3,700,000 Jordan/Egypt/Peru etc.
Sulphur 780,000 Saudi Arabia, Kuwait,
Iran, Iraq
Ammonia 440,000 Middle East
Sulfuric Acid As per need Japan/Gujrat
MOP 112,000 Canada, Peru
Urea As per need Oman

The solid raw materials are discharged and conveyed to their

respective storage areas by conveyors system of 3000 MTPH capacity(1500
MTPH for Rock Phosphate and 1500 MTPH for Sulphur). The above raw
materials are transported to the plant through conveyors and pipelines

5|Page
2. OVERVIEW OF H2SO4 MANUFACTURING
 2.1 SULFURIC ACID PLANT : The SAP unit of IFFCO
Paradeep is designed by M/s Lurgi GmbH, Germany ( one of the most
renowned know-how suppliers of sulphuric acid process technology
over the world.
The sulphuric manufacturing process involves contact process in
which sulphur is burnt to produce SO2 which is oxidized b catalytic
oxidation to SO3. This SO3 is absorbed in weak sulphuric acid to form
oleum, which is then diluted to form 98.5% H2SO4. For achieving
higher efficiency DCDA (Double Conversion Double Absorption)
process is adopted.

The main features of Lurgi DCDA plants are –

 High efficiency LURO burner with spinning cup to achieve high
efficiency of combustion, high specific furnace load and small
furnace volume
 Waste heat from combustion gas and conversion is utilized to
generate superheated steam at 60 kg/cm2 , 480o C
 Intermediate absorber and final absorber with packed tower for
high absorption efficiency.
 Double converter ensures higher conversion efficiency of SO2 to
SO3 and lowest slip of SO2 in stack gas
 Use of hanging type candle filter to arrest acid mist formed in
intermediate and final absorption tower.
 Efficient start-up procedure with Alkali Scrubber Unit for
absorbing unconverted SO2 .

 2.2 PRODUCTS :The designed amount products of Sulfuric

Acid Plant are listed below-

PRODUCT NAME SPECIFICATION AMOUNT

H2SO4 98.5%(by wt.) 2x3500 MTPD

HP STEAM 60 kg/cm2, 4800 C 1.2 Ton/Ton H2SO4

(superheated)
LP STEAM 4 kg/cm2, 1500 C 0.4 Ton/Ton H2SO4

SO2 content in tail gas < 2Kg SO2 per Ton of 100% H2SO4
Acid mist in tail gas Less than 50 Mg/Nm3

6|Page
 2.3 PROCESS DESCRIPTION : The solid sulphur(99.5%
pure) from the sulphur storage is conveyed to the to the sulphur
melting tanks after being dosed with lime to neutralize the free acidity
present in it. The melting tanks are provided with steam coils inside it
to provide required heat for melting by using saturated steam of
6kg/cm2 . Molten sulphur from melting tanks is filtered by three shell
and leaf filters followed by filtration in candle type ceramic filtration
unit. The filtered liquid sulphur (> 99.9% pure) is stored into molten
sulphur storage tank (MSST) at 1450C. From MSST, molten sulphur is
stored in a pump tank from where it is pumped by individual pumps
to the burners of each stream. The required air is filtered and dried in

Fig. Overview of sulphuric acid plant

drying tower(drying is achieved by counter-current contact of 98.5%

sulphuric acid and air) and supplied to the furnace by turbine driven
air blower. Some part of the air is supplied to the burner through
primary air fan, which atomizes the liquid sulphur for efficient
burning. The sulphur is burnt in the furnace at around 11000C, to
form SO2. After combustion, the product gas is cooled down to 4200C
in a water tube forced circulation waste heat boiler, where saturated
steam at 60 kg/cm2 is generated. The combustion gases from the
waste heat boiler pass through converter-1 and converter-2, which
contain V2O5 catalyst. Each converter has two beds of catalyst
through which the SO2 borne gases pass through and converted into

7|Page
SO3. The combustion gases from boiler are passed through the 1st bed
of converter-1 in which around 60% conversion is achieved. As the
conversion process is exothermic the gas coming out of bed 1 is at a
temperature of 6150 C. This is cooled down to 4350C in super heater 2
where partly superheated steam is further superheated to 4800C. The
gas from super heater-2 at 4350C enters the bed 2 of converter-1
where 83% conversion is achieved. The hot gas coming out from bed 2
is cooled down to 4300C in super heater1, where saturated steam from
the steam drum of waste heat boiler is partially superheated. The
cooled outgoing gas now enters the bed-3 of converter-2 and come out
at 4650C with around 95% conversion of SO2 achieved. This gas is
cooled down to 2160C in gas-gas heat exchanger ( hot and cold heat
exchanger respectively) and enter into an Intermediate Absorption
Tower(IAT) where SO3 is absorbed with recirculating 98.5% H2SO4. To
adjust the concentration of the circulating sulphuric acid, 96%
sulphuric acid from the air drying tower is added with it via control
valve. Part of the product generated in the IAT is pumped to the final
absorption tower as a function of the level in the pump feed tank
where the product is withdrawn from the final absorber. Another part
is returned to the drying tower via the level control of IAT.
Unabsorbed SO3 and SO2 coming out from the IAT is heated up by
passing it through the cold and hot heat exchangers respectively and
is fed to the bed-4 of converter-2, where 99.7% conversion of SO2 is
achieved. Hot gas coming out of bed-4 is cooled down in the
economizer where boiler feed water is preheated prior to feeding in
boiler. Cold gas coming out from economizer is sent to the final
absorption tower (FAT) where the SO3 is absorbed in recirculating
98.5% H2SO4. FAT is connected with a pump tank in which two
vertical submersible pumps are installed for acid circulation in tower
and one pump is installed for taking out the product acid and sending
it to the storage tank. Each recirculation pump discharge is routed
through tow plate type heat exchangers for cooling acid prior to
trickling in acid tower. To adjust the concentration in the final
absorption circuit, 96% sulphuric acid from air drying tower is added
via a control valve. At the top of FAT trickling system candle filters are
installed to arrest the mist formed. The gas leaving the candle filter of
the final absorption tower with acid mist concentration of 40 mg
SO3/Nm3 gas and SO2 concentration of <0.035% is routed through the
tail gas stack to the atmosphere.
The plant is equipped with alkali scrubber unit. The objective of
the scrubber unit is to treat the effluent gas during start up and
control the SO2 concentration within prescribed limit.

8|Page
 2.4 HEAT RECOVERY SYSTEM :
The Heat Recovery
System(HRS) absorbs SO3 from the gas stream and recovers the heat
from the absorption process as intermediate pressure steam (IPS). The
HRS is installed in between the cold heat exchanger and the initial
absorption tower.

Fig. Heat Recovery System

The HRS consists of the following –

Steam injection chamber
Packed heat recovery tower
Horizontal steam boiler
HRS heater
HRS preheater
HRS diluter
Acid circulating pump (located in the pump boot) and acid drain
pumps.

The HRS recovers heat in two stages-

 FIRST STAGE : The first stage recovers the heat of formation

of sulphuric acid. This stage includes the heat recovery tower,
boiler, heater and preheater
 SECOND STAGE : The second stage removes the residual SO3
and H2SO4 vapour, remaining heat of formation, heat of
condensation of H2SO4 vapour and sensible heat from cooling
process gas. The intermediate absorption tower serves as the
2nd stage of the HRS.

9|Page
3. DETAILED PROCESS DESCRIPTION
OF SULFURIC ACID MANUFACTURING
 3.1 MELTING AREA: The sulphur melting area is organized and
equipped to permit the safe handling of solid and molten sulphur to
provide the necessary clean feedstock of molten sulphur to the
sulphuric acid plant

Fig. Sulphur melting area

 3.1.1 SOLID SULFUR FEED : Solid sulphur is fed continuously into

the melting tank via feed hoppers, vibrofeeder and belt conveyor. A
central agitator installed in the sulphur melter recirculates liquid
sulphur through the heating coils. The solid sulphur is immersed
into sulphur stream and transported to the heating coils thus
ensuring a prompt and efficient melting of the solid sulphur

 3.1.2 SULFUR MELTING : The solid sulphur is transferred to the feed

hoppers by means of a front-end loader. Using belt conveyors, solid
sulphur is sent to the melting tanks. The sulphur is melted by
means of steam-heated tube bundles. The agitators are arranged in
the centre provides for uniform distribution of the sulphur in the
tanks.

10 | P a g e
Important points in sulphur melting operation

1. Inadequate heating of the sulphur piping and valves may lead

to clogging as a result of solidified sulphur. It is therefore
essential to see the functioning of the steam traps installed.

2. Sulphur(liquid) causes corrosion of the steam carrying pipes if

comes in contact with air. To avoid corrosion steam pipes are
graphite lined where molten sulphur comes in contact with air and
steam pipes.
3. It is important that the sulphur temperature is at all times
kept between 130-150OC. This depends on the pressure and
temperature of the heating steam. Saturated steam at 4
Kg/cm2(g) and temperature 145OC is used

4. Sulphur temperature is never allowed to go above 155OC because

in this range the sulphur becomes highly viscous and may lead to
pumping problem.

Fig. Viscosity vs. temperature of sulfur

11 | P a g e
 In order to attain desired melting results, the following parameters
are to be ensured –

A) All steam valves up to the heating coils are fully open; the
steam traps are in operation

B) Agitators in the melting tanks are in operation

C) The sulphur rate to each melting tank is to be such that

about 51 t/h sulphur are transported

D) For neutralizing the sulphuric acid contained in the

sulphur, lime is added by means of a dosing unit; the rate
(double stoichiometric value) is calculated on the basis of
sulphur amount and H2SO4 content as follows

mLime {Ca(OH)2} = mSulphur * c(H2SO4) * 1.5

(kg/h) t/h wt%

E) The temperature of the liquid sulphur is controlled by adding

steam to the heating coils. In case that the solid sulphur
amount added should not be in line with the melting capacity
which means if the sulphur temperature is too low while the
steam valve is fully open, it is essential to reduce the sulphur
rate

F) The melting tank filling level is controlled by means of an

overflow to the pump tank; the level is increased with
increasing sulphur rate. When the level rises it is necessary to
reduce the sulphur feed rate

 3.1.3 MOLTEN SULPHUR FILTRATION : Ash content in molten

sulphur may cause severe problem in down-stream process, like
they may cause pipe choking, deposit on catalyst bed that
reduces the conversion efficiency, so it is necessary to remove ash
from the molten sulphur. To remove the ash content from molten
sulphur, it is passed through primary and secondary filter.

Major consequences of molten sulphur filtration are as follows -

i. Premature fouling of catalyst bed
ii. Corrosion on down-stream line
iii. High viscosity effects on rate and efficiency

12 | P a g e
The molten sulphur coming out from the melting tanks are temporarily
stored in pump tanks. By means of the pumps installed in the pump
tanks, sulphur is extracted from this tank by pumping it through the
sulphur filter (primary leaf filter and secondary candle filter) where it is
filtered and the pure sulphur is transferred to the storage tank for
intermediate storage. Before entering the filter, molten sulphur is pre-coated
with filter aid.

In order to be able to achieve optimum filtration results, it is

necessary to abide by the following criteria:-

a. Filter coating correctly applied

b. Make sure that the filters are continuously fed with sulphur; if the
sulphur feed is interrupted, it is necessary to empty the filters and
apply again a filter coat; when the sulphur feed is restarted in this
case, unfiltered sulphur may leak into “pure sulphur tank”.

c. At a pressure in the filter of about 5.5 bar (g), stop filtration, empty
the filter, clean it and pre-coat it again

d. Make sure that the filters and the pertinent equipment are always
kept well heated

e. In principle, a filtering time of about 16 h/d has been planned as

well as 8 h/d for cleaning, pre-coating, etc.

 3.1.4 FILTERED SULPHUR STORAGE : The pure sulphur coming

from the filtering station is stored in Molten Sulphur Storage
Tank(MSST).The liquid sulphur(IOCL-sulphur) from the sulphur pit is
also stored here. From the storage tank, the liquid sulphur is
transferred to a vertical pump tank from which it is routed to the
sulphur burner by means of vertical submersible pumps.

In order to ensure proper operation, the following are to be

taken into account-

1. The storage tank is provided with level indicator. Under normal

conditions the melting and the filtration are to be controlled such
that the level in the tank is maintained in the upper third; in order
to avoid overfilling, it is necessary to reduce the capacity or
disconnect the sulphur melting/filtration units.

13 | P a g e
2. By means of installed heating coils, the sulphur temperature in the
storage tank is maintained at about 150oC; it is necessary to ensure
that the steam valves in the inlet piping are completely open; the
proper function of the condensate separators has to be ensured

3. The storage tank is connected with a vertical pump tank. The filling
level in the pump tank is maintained constant by adding sulphur
from the storage tank by means of control valve ; opening the valve
means a higher level; closing the valve means a lower level

 3.2 SULPHUR COMBUSTION: The Sulphur furnace is a

combustion chamber for the production of SO2 from molten
elemental sulphur. The burning of sulphur to SO2 requires no
additional fuel. Sulphur will “auto ignite” in the presence of sufficient
Oxygen (O2) at temperatures above 400oC. The combustion process
of sulphur is exothermic, which produces huge amount of heat that
heat is used to produce high pressure superheated steam (60
kg/cm2, and 4800C) in waste heat boiler system.

 3.2.1 THE BURNER SYSTEM :

LURO-Rotary Cup Atomizer- The burner is a specially

developed LURO-rotary cup atomizer. Liquid sulphur is fed to the
burners at 145OC through the pipeline which routes the liquid
sulphur to the sulphur distributor in the rotary atomizer cup of
each burner. The liquid sulphur supply line is equipped with a
steam heating system to ensure that the liquid sulphur is maintained
at an almost constant temperature. The sulphur is atomized
homogeneously by the rotary conical shaped atomizing cup burner
rotating in an axial flow of primary air. The atomizing cup is
mounted on a shaft which is connected with a belt to three phase
motor that rotates the shaft at 5200rpm.

Wind Box and Air Register - The wind box and air register,
guide and distribute combustion air (Secondary air).The wind box
inlet is connected to the air supply duct. A motor driven damper is
installed in the duct and used to control the air volume.

Air flowing through the secondary air annuls, is guided by

14 | P a g e
air vanes in to the combustion chamber where it collides with
atomized sulphur and combusts fully providing, as a result, the
required SO2 Content.

Fig. Sulphur Burner

Ignition - Each burner is equipped with a gas-electrical igniter

(ignition medium: LPG) which is used only during system heating
with HSD oil. Before sulfur is burnt, the igniter must be disassembled
and the installation opening has to seal. Gas for ignition purpose
is supplied through a pressure controller for each burner, from gas
cylinder. The ignition gas flow to each burner‟s igniter is closed or
opened by two solenoid valves fitted for each burner

Flame Detection - Each burner is equipped with flame detection

device that monitors the flame during the ignition and preheating
cycles. Before burning sulfur the flame detecting device must be
disassembled and installation opening has to be sealed.

Burner Data - The burner data are listed below-

Type SSK 2400 LURO

Design For sulphur furnace with rotary
cup atomizer
Sulphur Capacity Max. 24MTPH, Min. 8 MTPH

SO2 content 11.5% (vol.)

15 | P a g e
  3.2.2 Main Air Blower System : The compressor driven by a
backpressure turbine conveys atmospheric air dried in the dryer
tower to the sulphur combustion and the converter. The compressor
and the turbine are mounted on a joint base frame. The turbine and
the compressor are linked by gear box. The machines are provided
with tilting-pad friction bearings with hydrodynamic lubrication.

Details of steam turbine for main air blower is listed below-

Rated Capacity 6237 Kw

Design Speed 12586 rpm
Inlet steam condition 60 kg/cm2, 4800C
Exhaust steam condition 4 kg/cm2, 1950C
Direction of rotation Counter clockwise, seen
from turbine toward
coupling

Control oil pressure 8 bar

Lube oil pressure 1.5 bar

The oil is fed via an oil supply unit which also supplies the shut-
down valve on the turbine side via solenoid valve and oil pressure
switch thus allowing for a safe shutdown of the compressor/turbine
unit in case of a drop in oil pressure. The oil tank is located on the
base frame below the turbine.

The air volume required to adjust the plant capacity is

controlled as a function of the turbine speed.

During nominal load plant operation and when operating the plant with
sulphur in the lower load range, the turbine of the air compressor is fed
with the steam (61 Kg/Cm2(g), 480 oC) generated in the waste heat
recovery unit of the sulphur combustion unit. This steam is relieved in the
turbine to 3.5 Kg/Cm2(g) and fed into works grid. The temperatures, oil
pressures, vibrations and speed are controlled by meters. In case of
malfunction alarm signals are triggered or the compressor/turbine unit is
tripped.

The task of the air blower (or compressor) is to convey the dried
atmospheric air required for sulphur combustion as well as for the
heating up of the plant.

16 | P a g e
 PRIMARY AIR ( Drawn by
primary air
fan/compressor)

AIR(Drawn
by turbo
driven air
blower) SECONDARY AIR (Drawn
by wind box and air
register)

The task of the primary air compressor is conveying and pressure increase
of the air volume required to atomize the sulphur fuel oil in the LURO
burners taken from the pressure side down stream of the air compressor

 3.2.3 SULPHUR FURNACE : It is of carbon steel shell with inside

500mm.refractory lining. Combustion of sulphur takes place in the
furnace. On the dished end of the furnace burner wind box is
arranged. Sulphur burners are fixed on these wind boxes. Air flows
through the secondary air annulus, is guided by the air vanes of the
wind box into the combustion chamber where it collides with
atomized sulphur and combusts fully providing, as a result, the
required SO2.

Fig. Sulphur Furnace

17 | P a g e
  3.3 WASTE HEAT BOILER SYSTEM : The waste heat boiler
system is accommodated to produce high pressure steam by the heat
recovered from the combustion gases. This system is comprised of a
boiler, steam drum, economizer, superheater-1, superheater-2, de-
aerator and BFW( boiler feed water) pumps.

 3.3.1 DM Water handling and De-aeration : The boiler feed

water needs to be treated prior to feeding in the boiler for the following
reasons-
Prevention of hard scale formation on the heating surfaces
Elimination of corrosion
Control of carry -over of eliminated deposition on super heater
tubes.
Prevention of silica deposition for preventing turbine tube
damage

DM water coming from DM water plant is sent to the de aerator, DM water

is pumped from DM plant to SAP at 4Kg/cm2 pressure.

DM water inlet properties :-

DM water may contain excess dissolved oxygen and CO2 that cause
severe corrosion problem in the economizer section. The solubility of these
gases in water decreases with increase in temperature and becomes
zero at the boiling or saturation temperature. These gases are removed in
the de-aerator, where feed water is heated to saturation temperature by the
steam. In feed water system, it will contribute to metal transport in to the
boiler, where deposition can lead to under-deposit corrosion and long term
overheating. Dissolved oxygen enters the system via makeup water, which
is often air saturated, or leaks in to condenser or through pump seals.
Oxygen problem are especially severe where ammonia is present in
significant quantities. In presence of oxygen, ammonia is very corrosive to
copper. Ammonia is used for feed water pH adjustment. It can also be

18 | P a g e
formed from the thermal breakdown of hydrazine.

3N2H4 N2 + 4NH3

If oxygen is kept low by mechanical and chemical means then ammonia

will not be a problem for copper.

However, maintaining low oxygen level is quite difficult task by mechanical

or de aeration, so chemical oxygen scavengers is also applied to remove
trace of dissolved oxygen from feed water.

To neutralize the effect of residual dissolved oxygen and carbon di-oxide

gases in water, sodium sulphite[Na2So3]or hydrazine[N2H4]is injected in
feed water at the suction of the boiler feed water pump or in the de aerator
itself.

Hydrazine N2H4, being a strong reducing agent, has found wide

application in preventing corrosion in boiler. Hydrazine is available
either in hydrazine hydrate N2H4.H2O or hydrazine sulphate
N2H4.H2SO4 form. Hydrazine hydrate is colorless liquid, readily absorbs
from air CO2, O2 and moisture and has weak alkaline properties.
Hydrazine sulphate is a solid substance, poorly dissolves in cold water and
possesses acid properties. Hydrazine binds dissolved oxygen following the
reaction-

N2H4 + O2 = N2 +2H2O

which proceeds at an appreciable rate only at t ≥373oK. An increased PH

value also has an added effect on the reaction rate. At PH = 9 TO 9.5;
T=376to378OK and with a hydrazine excess of about 20µg/Kg it takes 2 to
3 seconds to bind O2.At PH< 7,hydrazine fails to control corrosion and even
intensifies it to some extent.

Hydrazine hydrate does not increase the content of solids in feed water
and yields no harmful volatile decomposition products.

For dosing of Neutralizing Amine + oxygen scavenger - L.P.Dosing pump is

used

19 | P a g e
  3.3.2 Feed Water Treatment : In the boiler, dissociation and
recombination of water goes on till the equilibrium is reached.

HOH = H+ + (OH) -

The presence of excess hydrogen ions makes the water acidic and hence
corrosive. The pH is the logarithm of the reciprocal of the hydrogen ion
concentration. If the hydrogen ion concentration in water is 10-7, the pH
value of water would be log (1/10-7) or 7. The pH of water varies with
temperature. At 150C the pH of neutral water is 7.If pH >7, water is
alkaline and if pH<7, it is acidic. A pH 10.5 is usually maintained for
boiler water in order to minimize corrosion. It will however, cause scale
formation. Two principle steps in scale prevention are –

1. Periodic or continuous blow down: Concentrated solid precipitated at

drum bottom (by chemical treatment) are removed through blowdown,
which may be either intermittent or continuous. The amount of blow-
down is governed by the allowable solids concentration and the purity
of feed water.

% Blow down = [Quantity of water blowdown/Quantity of feed

water]*100%

Blowdown water quality –

2. Chemical treatment of water: Trisidium phosphate [Na3Po4] is

added to prevent scale formation. In the boiler, these phosphates
react with calcium salts to form tricalsium phosphate, which is a
flocculent precipitate. The magnesium salts are also readily
precipitated due to alkalinity of boiler water.
5Ca+2 + 3PO4-3 + OH- 
Ca5 (OH) (PO4)3

20 | P a g e
 3.3.3 Boiler feed water handling- BFW pumps : The
purpose of this pump is to feed de-aerated water in boiler system. The
pump discharge is directly connected to the Economizer. After getting
partially heated, BFW goes to the steam drum and thereafter gets
distributed in the Boiler System.

Fig. Boiler Feed Water Pump

The details of the BFW pumps are listed below-

Quantity 04( 2 motor driven and 2 turbo driven)

Type Horizontal multistage centrifugal
( 6 stages)
Head 917.48m
Capacity 246.3 m3/hr
NPSH 8.6
Normal Speed 2974 rpm
Pump power input 763 kW
Suction Pressure 2.122 kg/cm2
Discharge Pressure 89.65 kg/cm2
Normal Efficiency 77%
Operating 1060C
Temperature

21 | P a g e
 3.3.4 Economizer : An economizer is a heat exchanger which
raises the temperature of the feed water to about the saturation
temperature corresponding to the boiler pressure. The term
„economizer‟ was used because the throwing away of high
temperature gases involved a great deal of energy loss. By utilizing
these gases in heating feed water, higher efficiency and better
economy were achieved and hence the heat exchanger was called
economizer.

 3.3.5 Waste Heat Boiler : The waste heat recovery system

comprises a forced circulation water tube boiler and a steam drum
located at the top. The boiler and the steam drum are connected by
way of risers and down comers. The boiler is arranged at a right angle
to the sulphur furnace. An outside gas bypass allows for the
adjustment of the required gas temperature to the inlet of the
converter during heating up and plant operation. The total heat
transfer area of the boiler is 3222 Sq. Mtrs. Through the boiler
system, the excess heat generated during the sulphur combustion is
recovered to generate high pressure super saturated steam. During
normal operation the feed water volume required in the boiler for
steam generation (105oC, approx. 74Kg/Cm2) to the lowest tube
bundle of Eco I where it is heated to approx. 230oC . Downstream of
the upper bundle of Eco I the feed water enters the boiler drum of
the tube evaporator at a temperature of approx. 260oC. The
saturated steam of approx. 70 Kg/Cm2 generated in the waste heat
boiler by heat transmission of the sulphur combustion ghases is
slightly superheated in the pre-superheater (superheater I) and then
superheated to the final temperature(superheater II). Part of the hot
steam of 60 Kg/Cm2 and 480oC is now routed into the back
pressure turbine to drive the air compressor. The other part is
supplied outside the plant battery limits.

 3.3.6 Super Heater I & II : The super heater is a heat

exchanger in which heat is transferred to the saturated steam to
increase its temperature. There are three types of superheaters
namely: radiant, convection, and separately fired.

A radiant superheater is placed directly in the

22 | P a g e
 combustion chamber
A convection superheater (used in our plant) is located in
the path of the hot gases.
A separately fired superheater, as its name implies, is
totally separated from the boiler

It reduces the moisture content of steam and thus the efficiency of

turbine is increased

The saturated steam of approx.70bar generated in the waste

heat boiler by heat transmission of the sulphur combustion gases is
slightly superheated in the pre-super heater [Superheater1] and then
superheated to final temperature of approx.480oc in two stages with
intermediate injection in Superheater-2.

Heating surface area of the boiler :-

EVAPORATOR 3222 M2

SUPERHEATER 1 1514 M2

SUPERHEATER 2 4326 M2

ECONOMIZER 5801 M2

23 | P a g e
  3.4 CONVERTER SECTION : The conversion of SO2 to SO3
takes place in converter section. There are two catalytic converters in
each train. The V2O5 catalyst required for the reaction to
generate sulphuric acid is distributed across 4 layers of the
converters (total 630 m3 equal to 180 l/tpd Mh). one two-layer,
stainless steel converter, and one two-layer brick lined converter.
Each converter has two beds.
Converter 1 – is of ASTM A 240 Tp. 304 H MOC along with the
internals. There is a central gas duct for conveying of gases.

Converter 2 – is of ASTM A 240 Tp. 204 Gr. B along with the internal.

In the design and construction of any converter intended to attain a

guaranteed maximum sulphur dioxide conversion, proper attention to
the removal of the very considerable reaction heat is of vital importance.
As the reaction is generally carried out under adiabatic conditions, the
temperature of the solid catalyst bed rises and consequently the attainable
SO2 conversion is limited in accordance with the thermodynamic
equilibrium. To achieve a high final SO2 conversion, the total catalyst mass
is divided up into several catalyst beds [trays] and the hot gas leaving each
bed is cooled before entering the next bed.

Fig. Typical Adiabatic Conversion Process

24 | P a g e
The converter 1 is made from stainless steel without refractory lining.
The trays are isolated with gas-tight separating domes. The converter 2 is
made from normal steel with refractory lining. The trays are isolated with
gas-tight separating domes.

Layer arrangement from top to bottom:

CONVERTER 1 CONVERTER 2

Layer 1 Layer 4

Layer 2 Layer 3

Whereby the flow direction in layers 1,2 and 4 is from top to bottom and
vice versa in layer 3. To support the catalyst, perforated catalyst trays have
been installed.

The sulphur combustion gases from the sulphur furnace (approx. 284000
Nm3/h; 11.5 vol % SO2) are cooled in waste heat boiler and routed with a
temperature of approx. 420oC to layer 1 of the converter. There, approx. 59
% of the SO2 reacts to form SO3 and the gas temperature rises to approx.
615oC due to exothermal reaction. In the downstream super-heater II the
gas is cooled to the inlet temperature for layer 2, i.e. approx. 435oC. After
layer 2 the gas is cooled in super-heater 1 from approx. 525oC to 430 oC. In
layer 3 the last conversion upstream of the intermediate absorption takes
place. The total conversion downstream of layer 3 is approx. 95% at an
outlet temperature at layer 3 of approx. 465oC. Downstream of the layer 3
the gas is cooled in the hot heat exchanger and cold heat exchanger in
counter-current to the gas from the inter mediated absorber to approx.
216oC. Absorption of the residual SO3 takes place in the hot
intermediate absorber and in the downstream intermediate absorption
tower. The SO2 gas downstream of the intermediate absorption tower has a
temperature of 90oC and is routed to layer 4 of the converter for further
SO2 conversion. Upstream of layer 4 the gas must first be heated to the
reaction temperature of 405oC on the shell side of the cold and hot heat
exchangers in counter-current to the SO3 gas from layers 1 to 3. The gases
from layer 4 are directly passed to economizer 1. The gas leaves layer 4 with
a temperature of approx. 430oC; at this point, the total conversion from SO2
to SO3 will account to min. 99.7%.

25 | P a g e
Total volume of the catalyst beds are 630 m3.

Catalyst details are given below :-

SHAPE Star Ring

COLOUR Yellow-Yellow brown
OD 12-14 mm
ID 3-4 mm
LENGTH 12-20 mm
COMPOSITION V2O5 with alkali sulphates
V2O5 : 7 %, K2O : 10.5%
BULK DENSITY 0.45 kg/ltr
IGNITION TEMPERATURE Min 3800C
OPERATING TEMPERATURE 420-6300C
THERMAL STABILITY Stable upto 6500C

Effect of temperature on equilibrium conversion is as follows-

26 | P a g e
 3.5 DRYING AND ABSORPTION SECTION : Gas
absorption is a mass transfer operation in which solute gas is
absorbed by means of liquid absorbent in which gas is more or less
soluble. Absorption tower consist of cylindrical vertical tower or
column equipped with the gas inlet and distributing space at the
bottom and at the top liquid inlet and distributing space and a
supported solid mass called packing material in packed tower. The
packing material is typically supported on self- supporting brick
dome with large open area so that flooding does not occur at the
support. In this plant, the acid absorption towers are for absorbing
the SO3 gases entering from the bottom of tower and acid is sprayed
from the top of the tower. The acid mist generated during the
absorption process is removed by means of mist eliminators. The
acid is sprayed from the top of the tower by means of acid
distribution system. This acid comes down through the ceramic
saddles placed in the towers.

 3.5.1 Absorption of sulphur tri-oxide : Sulphur trioxide

formed by the catalytic oxidation of sulphur dioxide is absorbed
in sulphuric acid of at least 98% concentration, in which it reacts with
existing or added water to form more sulphuric acid. The optimum
concentration of the absorber acid corresponds to the azeotrope, as
the partial pressure of SO3, H2SO4 and water vapour are then at
their lowest. At lower acid concentrations the water vapour partial
pressure is higher, and there is correspondingly higher risk that
sulphuric acid mist will form as a result of direct reaction of
sulphur trioxide in the gas phase with the water vapour above the
acid. At concentrations above the azeotropic point, the tail gas will
contain an increased amount of sulphur trioxide and sulphuric acid
mist on account of their greater partial pressure.

27 | P a g e
Above fig. shows the equilibrium vapour pressure of H2O, H2SO4 and
SO3 above sulphuric acid at 60oC in the concentration range of 85 wt. %
H2SO4 up to 20 % SO3 oleum.These vapour pressure curves are
important in designing air drying and SO3 absorption.

Mostly the absorbers are packed towers, usually operating in

countercurrent. The gases pass from bottom to top through a bed of
packing, which uniformly irrigated from the top with concentrated
sulphuric acid. The process gas leaving the converter system is cooled, first
in a gas-gas heat exchanger or a steam generator and preferably, in a
feed water preheater to a temperature of about 180-220Oc, before
entering the absorber. It is essential to ensure that wall temperature in
the gas coolers should never drop below the dew point [about 110-160OC,
depending on the gas composition], as otherwise there is an acute danger of
corrosion by condensing acid and mist formation. The gas entering the
absorber is therefore not completely cold and it gives up heat to the
absorber acid as it passes through the absorber, by the time it reaches
the outlet it is virtually at the same temperature as the incoming absorber
acid.

A substantial amount of heat is also generated in the absorber acid from

the absorption of sulphur trioxide and the formation of sulphuric acid,
and the acid temperature rises in consequence by a margin which depends
on the acid circulation rate.

Efficient sulphur trioxide absorption depends not only on uniform acid and
gas distribution in the absorber but also on keeping the temperature and
concentration of the absorber acid constantly at the optimum value. The
acid concentration is maintained constant by adding process water to the
acid leaving the absorber at a rate controlled by concentration measuring
device. The optimum acid inlet temperature depends on the design
conditions, but it is about 60-80OC in most plants. It is maintained by
indirect cooling.

Irrigated packed tower absorbers are not efficient at removing sulphuric

acid mist. In-spite of efficient air drying and optimum conditions for
sulphur trioxide absorption, it is often impossible to prevent mist
formation completely. Therefore specially designed mist eliminators are
installed above the tower distribution system to arrest acid mist to avoid
corrosion in the downstream heat exchangers and further mist
formation in the final absorber. Glass fibers of different degrees of
fineness are preferably used as the filter material.

28 | P a g e
The design principle of conventional absorption towers is similar to that of
drying tower. They have a welded cylindrical steel shell, which is lined
inside with acid-proof bricks and silica-based acid proof mortar. The
tower is additionally protected by PTFE sheeting sandwiched between the
shell and the multilayer brick-lining.

Sulphuric acid is a strong acid with characteristic hygroscopic and

oxidizing properties. The dehydrating effect of concentrated sulphuric acid
is due to the formation of hydrates. Several known hydrates are H2SO4.
H2O[84.5wt.%H2SO4],H2SO4.2H2O[71.3wt.%H2SO4],H2SO4.3H2O[64.5wt.%
H2SO4],H2SO4.4 H2O [57.6wt.% H2SO4],and H2SO4.6 H2O [47.6 wt.% H2SO4].

It is not possible in practice to manufacture sulphuric acid by absorbing

sulphur trioxide into water because the sulphur trioxide reacts with the
water vapor in equilibrium with the liquid, initially forming sulphuric acid
vapour.This quickly condenses as mist of very fine[sub-micron]droplets,
which are practically impossible to arrest. However, sulphuric acid itself
reacts with sulphur trioxide to form di-sulphuric acid[H2SO4+SO3
=H2S2O7]which is converted back to sulphuric acid by reaction with water.

H2S2O7+ H2O = 2H2SO4.

It is therefore possible to absorb sulphur trioxide in sulphuric acid of

98 % or higher concentration over which the partial pressure of water
vapour is very low and thus avoid the problem of mist formation. However,
because the vapour pressure of H2SO4 and SO3 increase steeply at
concentrations above 99% H2SO4, the optimum sulphur trioxide
absorption efficiency is in 98-99% sulphuric acid.

 3.5.2 Air Drying : Air drying is an important process step in

conventional contact plants. It protects the cooler parts of the plant,
such as heat exchanger, against corrosion by acid condensation. It
safe guards against the formation of sulphuric acid mist, which can
be very difficult to absorb subsequently. It also protects the catalyst
from the ill effects of acid condensation when the plant is shut
down for any reason. Therefore the operating performance,
especially the tail gas purity and the service life of the plant depend
in large measure on an efficient and reliable air drying system. In the
drying tower, the air is dried in counter current with fairly
concentrated sulphuric acid in irrigated packed tower. The sulphuric
acid is circulated. The residual water content of the air after drying

29 | P a g e
 corresponds theoretically to the partial pressure of water vapor above
the drying tower acid at the prevailing temperature and
concentration. For the purpose of achieving high drying efficiency,
the temperature of the irrigation acid is normally maintained at
50-60Oc.
A substantial amount of heat, not just the heat of dilution of the
sulphuric acid but also the heat of condensation of the water is
liberated in the air drying tower.

For this reason the circulated acid is generally cooled by indirect heat
exchangers before being recycled to the dryer.

 3.5.3 Drying Tower Design : The dryers used now-a-days are

vertical cylindrical towers. Their steel shell is lined with acid proof
bricks. A grate of acid proof material carries the packing. Normally,
Raschig rings or intalox saddles of ceramic material are used as
packing. The dryer design is determined by a number of interacting
parameters, such as the surface characteristics and geometry of the
packing, the packing height, the gas velocity and the irrigation rate.
The efficiency of moisture absorption by the sulphuric acid depends
mainly on the diffusion resistance in the gas/acid interface. The
gas flow velocity is best kept well above the region of laminar flow,
as this induces turbulence which not only lowers the diffusion
resistance but also improves the distribution of the liquid.
The lower limit on the irrigation density is set by the minimum
acid rate required for uniform wetting of the entire packing surface.
The maximum rate is defined by the flooding limit, which itself is a
function of the gas velocity and strongly depends on the type of
packing, packing size and liquid flow rate in the tower. It is to be
determined empirically for each packing type.

30 | P a g e
An essential prerequisite for uniform acid distribution over the entire tower
cross-section is the acid irrigation system. Preferably; the acid irrigation
system should be placed in the upper part of the packing. As a general
rule, a wire mesh filter is installed above the packing layer to separate the
entrained acid droplets.

 3.5.3.1 Acid Cooling System in Drying Tower : The acid

cooling system plays a vital role in determining the efficiency
and operating safety of the whole sulphuric acid plant. To
increase the overall efficiency of drying tower, as mention in
above section, circulated acid is cooled in plate type heat
exchanger and water is used as cooling medium.

 3.5.4 INTERMEDIATE ABSORPTION TOWER AND HRS :

The SO3 gas from layer 3 is cooled in gas heat exchanger and routed
to the HRS tower in train1 and in train 2 it is sent to the IAT. The
Heat Recovery System (HRS) absorbs SO3 from the gas stream and
recovers the heat from the absorption process as intermediate
pressure (IP) steam. The first stage recovers the heat of formation
of sulfuric acid. The second stage removes the residual SO3 and
sulfuric acid vapor, and removes the remaining heat of formation,
heat of condensation of sulfuric vapor, and sensible heat from cooling
process gas. The interpass tower serve as the 2nd stage of the HRS.
The HRS consists of a steam injection chamber, a packed heat
recovery tower, a horizontal steam boiler, an HRS heater, an HRS
preheater, an HRS diluter, an acid circulating pump (located in a
the pump boot), and acid drain pumps (2). The steam injection
chamber receives process gas from the existing acid plant. A portion
of the water required to maintain HRS acid concentration is
injected as low pressure steam (0.70 bar g, minimum) into the
process gas in the steam injection chamber. Steam injection has
several advantages: decrease corrosion rate in the first stage of the
HRS tower and reduce acid flow over the first stage thereby
reducing the size of the HRS diluter, HRS circulating pump and
first stage distributor. Steam for injection will be let down from the
outlet of the HRS boiler.

The heat recovery tower receives SO3 gas from the steam injection
chamber. SO3 is absorbed from the gas flowing upward through the
packing into circulated sulfuric acid flowing downward through the
packing. The partially cooled gas, with the remaining SO3, exits the HRS

31 | P a g e
tower and enters the existing interpass tower. The process gas flows
upward through the existing interpass tower packing, where essentially all
of the remaining SO3 is absorbed into circulated sulfuric acid flowing
downward through the packing. Acid from the first stage collects in the
base of the tower and is circulated via a vertical, submerged, centrifugal
pump installed in the pump boot.

Gas from the interpass tower flows through re packed mist eliminators
installed in the top of the tower, and then to the existing heat exchanger.
These mist eliminators remove acid mist formed in the towers down to a
level equal to that of conventional interpass absorbing tower mist
eliminators, to protect the downstream heat exchanger.

Acid is pumped from the HRS tower pump boot to the horizontal boiler.
From the boiler, most of the cooled acid flows to the HRS diluter and then
back to the first stage of the HRS tower. A small stream, corresponding to
the acid volume produced in the tower and any crossflow from the drying
tower, is further cooled in the HRS heater and HRS preheater where
heat is transferred to the HRS boiler feedwater and treated water,
respectively. From the HRS preheater, the acid flows to the existing acid
system, where it is mixed with acid from the other towers.

Cooled acid from the existing acid cooler is supplied to the interpass
tower at 98.5% minimum strength.

Dilution water is continuously mixed with acid downstream of the HRS

boiler to control acid strength to a minimum of 99.0%. The acid is then
circulated over the HRS tower first stage. The addition of dilution water
and the resulting absorption of SO3 raises the temperature of the
circulated acid due to the heat of formation. As acid is circulated
through the boiler, this heat is exchanged with boiling water. To provide a
temperature driving force for heat exchange in the boiler, the acid is
circulated at temperatures above the boiling point of the steaming water.

During periods of high humidity the amount of water vapor in the air
entering the drying tower may be greater than the amount of H2O
required to control the final tower and product acid strength at 98.5%.
At these times, increased flow of hot acid from the existing acid system
will be sent to the HRS diluter.

The HRS diluter is a Teflon lined stainless steel vessel.

The maximum recommended concentration for HRS circulated acid is

99.7%. At concentrations above this level, SO3 absorption in the HRS
tower decreases, resulting in reduced heat recovery. Because of the

32 | P a g e
importance of concentration control, the HRS analyzers will utilize a TFE-
lined, flow through conductivity cell that is mounted externally on the
sample lines. This eliminates the problem of probe breakage and
erroneous readings from inadequate sample flow.

A comprehensive system of interlocks (actuated by acid temperature,

strength, and flow) is provided to prevent continued operation with acid
strength below the recommended minimum concentration of approximately
98.5% to the first stage.

The HRS boiler‟s continuous and intermittent blow down effluent is

flashed to the atmosphere in the HRS boiler blow down flash tank and
drain discharge is taken to the process sewer.

 3.5.4.1 ACID COOLING : Shell and tube heat exchangers are

used to cooling purpose of circulating acid in tower to achieve
optimum absorption of SO3 gas in tower. Absorption of SO3
is an exothermic process that increase the temperature of the
absorbent (Sulfuric acid) that need to cool down at the
required process value.

SHELL AND TUBE COOLER :- Shell and tube heat exchangers consist of
a series of tubes. One set of these tubes contains the fluid that must be
either heated or cooled. The second fluid runs over the tubes that are
being heated or cooled so that it can either provide the heat or absorb the
heat required. A set of tubes is called the tube bundle and can be made
up of several types of tubes: plain, longitudinally finned, etc

ANODIC PROTECTION COOLER :- The rate of corrosion of unprotected

stainless steel components by sulphuric acid rises sharply with the
temperature, but this can be compensated by anodic protection, which
substantially reduces the linear corrosion rate, even at temperature well
above 100OC. The Acid Coolers for increased acid temperatures and waste
heat recovery are provided with an anodic protection system. In case of
wall temperatures of material higher than 70 oC, the corrosion rate
increases considerably, because the material surface attains to an
uncontrolled, unstable, active condition. The anodic protection system has
the function to build up the passive coating on the surface of the heat
exchanger to be protected, to preserve it and to ensure a low uniform
corrosion rate. For an anodically protected cooling system, the acid cooler
is the anode (positive pole) whereas especially tube cathodes in the acid
cooler from the cathodes (negative pole). These cathodes are electrically
insulated from the acid cooler. The required potential of the anode is
maintained by the potentionstatically operating anodic protection panel and

33 | P a g e
is controlled by a reference electrode. Besides the control reference
electrode at acid inlet, further reference electrodes are applied for
measuring the single potentials of the anodic protection system. The
sulphuric acid must be handled free of bubbles. Gas holes resp. two-phase
currents impair the formation of homogeneous passive coats. Besides that,
loadings due to solid substances, which might occur in spite of
strainers installed, may lead to increased corrosion velocities and thus
higher linear corrosion velocities. An increased halogen content can lead to
corrosions also in the passive area. To prevent this, the plant has to be
cleaned (flushed) at regular intervals. Larger solid particles or deposits
will rapidly cause the destruction of the cooler because of erosions and
missing or disturbed passive coat. It is therefore urgently required to
install strainers (mesh diameter < 6 mm, with a flow face equal in section)
before cooler. The customer is recommended to issue an operating
instruction especially made up for the workshop to enable the operating
personal to take quick logical actions in case of any disturbances.

 3.5.5 FINAL ABSORPTION TOWER : The SO3 generated in

layer 4 of the converter from the residual SO2 is absorbed in the
final absorber in an approx. 98.5% sulphuric acid. The structure of
the final absorption circulation with a pump feed tank two acid
pumps (immersion pumps) for circulation and acid coolers (plate-
type heat exchanger) is identical with that of the intermediate
absorption tower.The produced acid is pumped through a product
cooler to the sulphuric acid tanks. To adjust the acid concentration
in the final absorption circuit, 96% sulphuric acid from the air dryer
is added via a control valve. The gas leaving the candle filter of the
final absorber with a sulphuric acid concentration of max.40 mg
SO3/Nm3 and an SO2 concentration <0.035 vol % is routed through
the tail gas stack to the atmosphere.

The dryer and absorber are equipped with traps to prevent level changes
in the acid system in case of load changes/pressure changes. In other
words, the acid, levels in the towers practically remain constant at all load
phases with the acid pumps in operation, that is, their level remains
approx. in the center of the acid discharge. This also prevents level changes
in the pump feed tanks.

34 | P a g e
  3.6 ALKALI SCRUBBING SYSTEM : In Sulphur based
Sulphuric Acid plant, sulphuric acid is produced by, burning sulphur
to SO2, conversion of SO2 to SO3 and consequently absorption of SO3
in H2SO4 and finally producing H2SO4. Almost all the SO2 liberated
should be converted to SO3 and the little amount of SO2 should be
left for stack. In normal plant running situation converter beds
catalyst temperature is maintained such that to convert almost
all SO2 to SO3 and remaining / unconverted the little part of SO2
is emitted through stack within restricted / statutory limit. But
whenever plant is started after shut down or after long stoppage,
catalyst temperatures are not sufficient to convert almost all SO2 to
SO3. In such cases unconverted SO2 increased and emitted SO2
through stack may exceed the prescribed limit. For prevention of
excess emission of SO2, the same is absorbed to the maximum extent
in ALKALI SCRUBBER, and SO2 emitted in atmosphere within
statutory limit. As per Pollution control board norms. The max.
limit of, SO2 to be emitted in atmosphere is 400 ppm or 2 kg / ton
of H2SO4 produced and, 50 mg/NM3 of Mist.

In IFFCO Paradeep plant Alkali scrubbing section is designed for

scrubbing 120000 NM3/hr of gas containing less than 2% of SO2 .
Normal duration hour of alkali scrubber is 6 hours or till SO2
concentration in outlet gas during start-up reduces to less than 400
ppm. Required quantity of sodium hydroxide of 40% concentration is
diluted by adding process water in scrubbing tower. This is analyzed
and controlled by taking sample and analysis done in laboratory. The
pH of the solution initially should be 11.0-12.0 The said Alkali solution
is circulated through scrubber pump in scrubbing tower which is
equipped with solution distribution pipes, and mist eliminator

SCRUBBING PROCEDURE :- During the start-up of sulphuric acid plant

the tail gas coming from Final absorption tower enters from bottom of
scrubber and rises to the top of scrubber. In the scrubbing section
Sulphur Dioxide gas comes in to contact with circulating scrubbing
solution and clean gas is vented to the atmosphere.

Primary reactions involved are as follows.

2NaOH + SO2 = Na2SO3 + H2O

Na2SO3 + SO2 +H2O = NaHSO3

The Mist in the gas is removed in poly propylene fiber bed mist
eliminators installed above the packing. The pH of circulating solution is
monitored continuously and initially it should be 11.8-12.0 after

35 | P a g e
absorption of SO2 pH should not be less than 8.0.If required make up
of caustic lye solution is done. This is monitored by pH indicator and
controllers and maintained by operating the control valves of caustic lye
and process water.

Whenever temperature of catalyst beds stabilizes for SO2 conversion and

FAT outlet gas containing SO2 is < 400 ppm or below environment norms,
the related dampers are operated to allow the gas to be vented directly
through chimney. Scrubbed solution is transferred to the scrubbed
solution tank and level of tower is minimized and then scrubber pump
is stopped.

AERATION : Scrubbed solution contains mainly sodium sulphite and

sodium bisulphite, which cannot be let out in drain directly. Scrubbed
solution from scrubbed solution tank is transferred to the aeration /
effluent tank. Aeration of scrubbed solution is started by agitating the
solution and providing oxygen through compressed air. During aeration
sodium sulphite and sodium bisulphite is converted into sodium sulphate to
the maximum extent.

Reactions that take place in the aeration section are

Na2SO3 +½ O2 = Na2SO4

2NaHSO3 + O2 = Na2SO4 +H2O

After starting the aeration effluent sample from top and bottom of tank
is analyzed for sodium sulphite and sodium bisulphite. If the presence of
sodium sulphite and sodium bisulphite is negligible then letting out the
effluent can be started. If the sample shows the presence of sodium
sulphite and sodium bisulphite even after reasonable aeration, then
aeration is continued till the desired value and then effluent is let out in
the drain. Effluent is to be drained in controlled manner by operating the
drain valve of effluent tank, say 2-4% of the level of the Final Effluent
Tank per hour. This may be decided based on the down steam of effluent
stream.

36 | P a g e
 4.FIRE AND SAFETY RULES
 4.1FIRE AND SAFETY :
Safety is the first step in any industry. Fire is the most common serious
hazard that one faces in a chemical industry.One must know the basics
about fire extinguisher- types ,how to use them, when and when not to use
them as well as proper procedure to follow with a fire emergency.

 4.2 TYPES OF FIRE EXTINGUISHER:

The two most common types of fire extinguisher laboratories are pressurized
dry chemical and carbon dioxide extinguishers . We may have other “clean
agent” extinguishers particularly if the workplace has sensitive electronic
devices such as computers .Those who work with flammable metals may
also have a specialised class D powder extinguisher for use on fires (in a
pinch, a bucket of dry sand will do, but one really should have a class D
unit if he works with such materials). Water filled extinguishers are not
acceptable for chemical laboratory use. If one has a water filled extinguisher
, have it replaced immediately by contacting campus or corporate fire
marshal‟s office.

KINDS OF EXTINGUISHERS :
 Class A fires are ordinary materials like burning paper , lumber,
cardboard, plastics etc .
 Class B fires involve flammable or combustible liquids such as
gasoline, kerosene, and common organic solvents .
 Class C fires involve energized electrical equipments such as
appliances ,switches, panels, boxes, power tools, hot plates and
stirrers .Water can be a dangerous extinguishing medium because of
the risk of electrical shock unless specialized U
 Class D fires involve combustible metals, such as Mg, Ti, K and Na as
well as pyrophoric organometallics reagents such as alkyllithiums ,
Grignard‟s reagent and diethyl zinc .These materials burn at high
temperature & react violently with water, air, and/or other chemicals.

USING FIRE EXTINGUISHER:

Use a mental checklist to make a fight –or-flight decision .Attempt to use an
extinguisher only if all of the following apply:

37 | P a g e
 The building is being evacuated (fire alarm is pulled)
 The fire department is being called(dial 101)
 The fire is small, contained and not spreading beyond its starting
point.
 The exit is clear ,there is no imminent peril and you can fight the fire
with your back to the exit.
 We can stay low and avoid smoke
 The proper extinguisher is immediately at hand.

 4.3 GENERAL SAFETY RULES:

 Employees must report all accidents immediately to their supervisor.

 Any defective or unsafe equipment must be reported to a supervisor
so that it may be repaired promptly.
 Confirm to all safety rules, sign and regulations .If the rules are not
understood then a supervisor shall explain them .
 Any unsafe conditions must be reported to a supervisor and
corrected , if within the person‟s responsibility.
 A safety belt with life line properly attached , anchored and adjusted
must be worn when working at a location without guardrails or
substantial barriers ,if the location is more than 2 m above a lower
floor or ground floor.
 Access to fire extinguishers or other fire fighting equipments must
not be blocked.
 Equipment must not be operated in an unsafe condition.
 Electrical repair must be made only by authorized personnel.
 Never watch any welding without wearing protective glasses.
 Objects must not be thrown or dropped from high places unless a
watchman has been posted below and if possible , the area has been
roped with appropriate signs.
 Compressed air must not be used to blow off any part of the body or
any clothing while it is being worn, except at authorized locations.
 Gasoline shall be used for fuel in motor vehicles similar equipment ,
and not for cleaning purposes or staring fires under any
circumstances.
 Wrist watches ,rings, and other metal jewelry must not be worn
while working or near energized circuits.

38 | P a g e
 5.ASSIGNMENT
PROBLEM 1 : FIND THE AMOUNT OF SULPHUR
REQUIRED TO PRODUCE 1 TON OF SULFURIC ACID ?

SOLUTION : Main reactions : S + O2 SO2

SO2 + ½ O2 SO3
SO3 + H2O H2SO4
OVERALL REACTION :S +3/2 O2 + H2O H2SO4
1 kmol sulphuric acid needs 1 kmol sulphur as per the
reaction
M.W of H2SO4 = 98
M.W of S =32
Thus 98 kg of sulphuric acid requires 32 kg sulphur
Thus 1kg of sulphuric acid needs 32/98 kg sulphur
Thus 1000 kg sulphuric acid needs 32/98 *1000 kg
sulphur
= 326.531 kg
sulphur
Thus 1 ton sulphuric acid needs 0.33 ton of sulphur.
(Assuming 100 % conversion and 100% absorption)

39 | P a g e
PROBLEM 2: Find the amount of air and volume of air
required to produce 1 ton of sulphuric acid if oxygen is
taken as 10% excess?
SOLUTION :

Main reactions : S + O2 SO2

SO2 + ½ O2 SO3
SO3 + H2O H2SO4
OVERALL REACTION :S + 3/2 O2 + H2O H2SO4

1 kmol of sulfuric acid needs 1.5 kmol of oxygen

M.W of H2SO4 = 98
M.W of S = 32
Thus 98 kg sulphuric acid needs (1.5 * 32) =48 kg oxygen.
1000 kg of sulphuric acid needs 48 *(1000/98) =
489.796 kg oxygen
For 10% excess oxygen required is 1.1* 489.796 kg =

538.77kg
MOLES of oxygen required is 538.77/32 = 16.84 kmol
Since air contains oxygen of about 21 % thus oxygen
needed is
16.84/0.21 = 80.20 kmol
M.W OF AIR = M.W of nitrogen* 0.79 + M.W of oxygen
* 0.21
= 28*0.79 +32*0.21
= 28.84 kg
So air required is 80.2* 28.84 = 2312.968 kg air
Volume of air required at N.T.P = 24*80.2 = 1924.8 m3

40 | P a g e
PROBLEM3.Make overall material balance on the system
and compare actual sulphuric acid production for the day
with production as per calculation?
SOLUTION:
Production of 25th Dec ,2016
SAP TRAIN -1
Sulphur – 1014.9 ton/day
Acid - 1681.4 m3
Now 1 kmol sulphuric acid needs 1 kmol sulphur as per the reaction
M.W of H2SO4 = 98
M.W of S =32
Thus 98 kg of sulphuric acid requires 32 kg sulphur
Thus 1kg of sulphur needs (98/32) kg sulphuric acid
Thus amount of sulphuric acid that should be produced (assuming
100% absorption and 100% conversion of SO2 to SO3 = 98/32*1014.9
=3108.13125 MTPD
From the data recorded Average SO2 released per ton sulphuric acid
=2.4642
Average SO2 per ton of sulphur = 2.4642/.33 (as 1ton H2SO4 needs
0.33 ton sulphur)
Total SO2 released = 2.4642/0.33 *1014.9=7.57853 MTPD
S lost = 7.57853/2 =3.789265 MTPD
This S would have led to production of (3.789265/0.33) H2SO4 i.e
11.4826 MTPD
So amount of H2SO4 production should be =3108.13125-11.4826 =
3096.64865 MTPD
Actual acid production from the data = 1681.4 m3 * 1.84 kg/m3

Difference = (3096.64865- 3093.776) = 2.87265 MTPD H2SO4

This amount of H2SO4 corresponds to 2.87265* (32/98) = 0.938 MTPD
Sulphur is lost/ not used in production of sulphuric acid.

41 | P a g e