PROJECT REPORT

Department of chemical engineering

Project on

DESIGN OF A PLANT TO MANUFACTURE SULFURIC

ACID FROM SULFUR
Submitted by

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ACKNOWLEDGEMENT
The Design Group would like to express their gratitude to Professors of the chemical
engineering department of Chandigarh university for the support, guidance and valuable
supervision provided in the course of conduction of this project.

All the data used in the project had been received from the Shreve and Norris book and the
Ceylon petroleum corporation and the rest things from world wide web.

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Contents

Introduction
Sulfuric acid - Background
Manufacture of Sulfuric acid - Evolution
Applications of Sulfuric acid
Availability of raw material
Existing process of manufacture
Lead Chamber Process and its development
Contact process
Process selection
Block diagram of selected process
Material balance

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 INTRODUCTION

Sulfuric acid

The properties of Sulfuric acid vary depending upon its concentration. Direct contact of Sulfuric
acid with anything from tissues (e.g. skin and flesh), metals, to stones will lead to their
degradation while a more acidic concentration will lead to their degradation in the form of
corrosion. Concentrated forms of the acid have strong dehydrating and oxidizing properties .

information on Sulfuric Acid

Alternate names Oil Of Vitriol, Hydrogen Sulfate

General appearance/qualities dense, clear (colourless), oily, corrosive
liquid
Specific gravity (25° C) 1.83 (Pure Sulfuric acid)
Freezing point 10.37° C (Pure Sulfuric acid)
Boiling point 338° C (98.3% conc. acid at 1 atm)
Commonly supplied concentrations 78%, 93%,98%
Related solutions Oleum (Fuming Sulfuric acid)

Dilute solution of sulfuric acid show all the behavior characteristics of acids. They taste sour,
conduct electricity, neutralize alkalies and corrode active metals with the formation of hydrogen
gas. From sulfuric acid, one can prepare both normal salts containing the sulfate group (SO4)-
and acid salts containing hydrogen sulfate groups (HSO4)

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Manufacture of Sulfuric acid – Evolution
Earliest days: Records of a compound similar to Sulfuric acid in its most primitive form had
started emerging from around the 16th century. General information gathered during the
literature survey about how Sulfuric acid came to be what it is today, point towards one Johann
Van Helmont who had employed destructive distillation3 of green vitriol (Ferrous Sulfate) and
burning of Sulfur to synthesize what had then been referred to as ‘Oil Of Vitriol'.
Beginning of Industrial scale production: In the 1790s Sulfuric acid had been manufactured
mainly for the Leblanc process for making Sodium Carbonate. Johann Glauber had pioneered the
process of by burning Sulfur with saltpeter (potassium nitrate) in the 17th century (History of
Sulfuric Acid, 2012) . Where previous production had mainly been lab scale based, it was during
this time that the economic value of Sulfuric acid has started being realized among industry
visionaries. But the best days of Sulfuric acid had still not come to pass.
Breakthrough: The development of the Lead Chamber Process by John Roebuck in the mid
18thcentury was a milestone in Sulfuric acid production, as it afforded the industry to increase
production capacity; even more significant about this was that the process was deemed far more
economically viable than any other processes hitherto developed for Sulfuric acid. The following
decades saw further improvements to the said process – where increased recovery of Nitrogen
Oxide was achieved, thereby contributing towards the overall improvement of the Lead Chamber
Process.

Pinnacle: The evolution of Sulfuric acid production reached its climax in the beginning of the
19th century, where Phillips, in Bristol, England, patented the oxidation of SulfurDioxideinto
SulfurTrioxide over a Platinum catalyst at high temperature. In other words, this was the
beginning of the development of the Contact Process, by which almost all of today’s Sulfuric
acid demand is met. The popularity of the contact process also improved the lead chamber
process, due to competitive advances of the production industry. The increased demand for more
concentrated forms of the acid (which was far easier and more possible with the Contact Process
than the Lead Chamber Process), coupled with lower costs of production associated with using
cheaper catalysts and the resulting lower price led to increase in popularity of the Contact
Process and the decline of application of the Lead Chamber Process.
Though the basic principle of the contact process remains unchanged to this day, with the dawn
of the 20th century, the contact process underwent the following improvements -

Replacement of catalyst: An even cheaper option for the catalyst was successfully
implemented – i.e. Vanadium Pentoxide. V2O5 also had the added advantage of being more
robust to catalyst poisoning and subsequent deactivation.
The development of the wet contact process by Lurgi: The catalyst was used for converting
Sulfur Dioxide containing gases having moisture. Further the air used for oxidizing Sulfur
Dioxide need not be dry. With this the capital and operation cost for the plant was reduced due to
reduction of drying machinery equipment, heat recovery systems, reduction in cooling water and
by-product production.

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Applications of Sulfuric acid
Sulfuric acid is widely used in industry because of its most important chemical and physical
properties. Other acids have similar properties but the relative low cost of sulfuric acid makes it
the most economical choice for wide variety of chemical application and these operations can be
classified by the particular property of sulfuric acid involved.

1. Sulfuric acid is an active acid with a high boiling point. The manufacture of halogen acids
namely HCl, HF etc and pickling of still make use this high boiling point. Leaching ores in the
manufacture of a metal pigment is more effective with sulfuric acid because high leaching
temperatures can be used without loss of acid by volatilization.
2. Sulfuric acid has great affinity for water. It is widely used for drying gases containing
moisture (Ex-Cell Chlorine). Virtually complete removal of water vapor from these gases is
accomplished by simple scrubbing operation.
3. Sulfuric acid forms hydrolysable sulfates with many organic compounds. Many alkylation
operations of petroleum and petrochemical industries depend on the ability of this acid to react
with hydrocarbons to form intermediate compounds. Aromatic alkylamines important to dye,
photographic and pharmaceutical industries are manufactured with sulfuric acid. The production
of industrially important synthetic alcohols is also based on this sulfuric acid property.
4. Sulfuric acid has special catalytic properties, probably related to its affinity for water. These
catalytic properties account for its large volume use in the manufacture of aviation gasoline.
5. Oleum is used in the manufacture of organic sulfonates. These materials used in large
quantities are major ingredients of the household detergents. Smaller quantities of special
sulfonates are used as lubricants and as additives to automotive lubricants.
6. Teamed with relative low cost as a marked advantage of sulfuric acid is the availability.
Sulfuric acid in the strengths (99 to 99%) common to commerce, doesnot reacts appreciably with
steel. Special containers are needed to transport commercial grades of Hydrochloric acid and
Nitric acid, but sulfuric acid can be transported in steel tank cars and tank trucks or shipped in
steel drums.
7. Sulfuric acid is widely used in the acidulation and neutralization processes because it is
frequently the most economical acid available for a particular purpose. The widespread use of
Sulfuric acid for pH control, which can be performed satisfactorily by any acid, is a direct result
of its low cost and its availability. The manufacture of phosphate fertilizers is the single largest
use of sulfuric acid. Large amounts of sulfuric acid are used in acid Coagulation Process (Ex-
GRS Synthetic Rubber) and in the regeneration of cationic exchange equipment. Other major use
include as the neutralizing agent is the production of synthetic fibers

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Availability of raw materials
Raw material souring is a main feature that limits the plant capacity. Since Sulfur is the
predominant raw material for Sulfuric acid manufacturing, other than those that produce the
latter in the form of recovering oxides of Sulfur, particular attention was given during the
literature survey to review sources and procurement of Sulfur.

Sulphur mines

Petroleum cracking

Metal pyrites

1) Galena
2) Saphalrite
3) Iron pyrite
4) Copper pyrite

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EXISTING PROCESS ROUTES FOR SULFURIC ACID
there are two main processes for manufacture of Sulfuric acid that are adopted at plants
across the globe as mentioned below.

1. Lead chamber process

2. Contact processes

However, minor variations within these main two processes also exist. Further, there are also
other processes which are not as popular in the industry, as the top two processes were, such
as,

● H2O2 process

● Activated Carbon process

As far as the contact process is concerned the literature review pointed out 3 different
processes that are based on the general operating principle of the contact process.

1. Single contact process

2. Double contact process

3. Wet Contact Process (WCP)

Lead Chamber Process and its development

As mentioned under sections above, this was a crucial development in the development of
viable production processes for Sulfuric acid. John Roebuck and Samuel Gardner introduced
a method to produce the Sulfuric acid in lead lined chambers.

Typical steps and reactions of the lead chamber process are as follows .

Step 1 - Burning of KNO3 (potassium nitrate/niter/saltpeter) and Sulfur in lead chambers:

Sulfur is oxidized by KNO3 and produces SulfurTrioxide. It works as an oxidizing agent and
provides oxygen to the reaction:

6 KNO3(s) + 7 S(s) -----> 3 K2S + 6 NO (g) + 4 SO3(g)

Step 2- In presence of water, the SulfurTrioxide converts to Sulfuric acid.

SO3(g) + H2O(l) -----> H2SO4(aq)

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This batch process was the original lead chamber process that John Roebuck and Samuel
Gardner introduced at 1746. At that time no air was introduced to the lead chambers during
the reaction. Later the continuous addition of air was suggested by Clement and Desormes. In
addition to that at about 1806 they defined the action of KNO3 in the lead chambers.

In 1835, the process of recovering Nitrogen from Nitrogen Monoxide was introduced by
Joseph Gay Lussac. This proved to be very important for reduction of KNO3 as a source of
Nitrogen. The reactions recovering Nitrogen was more important to limit the usage of KNO3.
This was one of the economically important factors that made the Lead Chamber process
more attractive then. KNO3 being expensive, the material cost reduced due to reduced
amount of KNO3. The recovery reactions are follows,

Step 3 - Produced nitrogen oxide reacts Oxygen in presence of water, giving Nitrous acid.

4 NO(g) + O2(g) + 2 H2O(l) -----> 4 HNO2(l)

Step 4 - Produced Nitrous acid react with SulfurDioxide for produce Sulfuric acid as the
main product. In addition the Nitrous Oxide formed would be reusable.

4 HNO2(l) + 2 SO2(g) -----> 2 H2SO4(aq) + 4 NO(g)

Due this improvement of the process, KNO3 requirement was limited to topping up the
Nitrogen amount. Further developments were added to the lead chamber process and the
operating cost reduced with them.

Modern Lead Chamber Process

Step 1 - Sulfur and KNO3 is burnt in the Sulfur burner and the KNO3 burner. SO2 is
provided to the lead chambers in two ways

1. Burning of elemental Sulfur with air and producing SO2.

2. Burning of Sulfur containing ores

The heat energy required to melt the Sulfur and KNO3 results in the final product of SO2,
NO2 and NO being at a temperature over 1000oC.

The burning of Sulfur done in one of two ways as indicated below:

1. Melting the Sulfur in a Sulfur smelter and pumping the molten Sulfur into the reactor to be
sprayed from the top. Air stream is provided countercurrent to oxidize Sulfur.

2. Sulfuris burnt directly to react with air in the Sulfur burner and the resultant SO2 stream is
taken as the output of the reactor.

Nitrogen can also be provided in two ways:

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1. Decomposition of niter at high temperature in presence of the acid.

2. Air oxidation of Ammonia to Nitric Oxide in the presence a catalyst.

Step 2 – Next, the products from the burners are filtered. The modern chamber process has
three main towers:

1. Glower tower

2. Lead chambers

3. Gay- Lussac tower

Hot SO2 gas is entered from the bottom of the glower tower and the Nitrogen oxide gases are
entered from the up and are set to flow as counter current liquid flow. In this tower the oxides
of Nitrogen are removed from the Sulfuric acid. At that reactor SO2is mixed and reacted with
Sulfuric acid with NO and NO2. This has the following features:

Concentration of the chamber acid and stripping of Nitrogen Oxides from the liquid to the
gas is occurred at this tower. Concentration of the chamber acid is achieved from the
evaporation of water from the acid. This is owing to the hot gases entering the glower tower.
The hot gas evaporates a considerable amount of water in the chamber acid. The
concentration of the acid output works out to be about 62-68 % Sulfuric acid according to
literature. Some amount of SO2 reacts with the hot air containing O2 and is oxidized to
SO3.The produced SO3 is dissolved in the acid being produced in the glower tower.

The dissolved Nitrogen Oxide is stripped from the acid and is conveyed along the outlet
gas stream of the glower tower.

Step 3 - This outlet gas stream is conveyed to the lead chambers which gives the process its
name, wherein it is first set to react with water (in the lead lined rooms). At the lead
chambers the reaction mix is subject to a series of reactions. Due to this complexity there are
usually three to twelve lead chambers in series. The gas is set to pass though all lead
chambers. The formed acid is condensed on the walls and collected on the floor of the lead
chambers. This formed acid called the chamber acid.

Step 4 - After the lead chambers, the gases are sent to the Gay- Lussac tower. It is essentially
a reactor where any traces of acid contained gases are ‘washed’ off. Further, in this tower the
nitrous vitriol forms from the reaction of remaining SulfurDioxides and Nitrogen Oxides.
This nitrous vitriol can be used in the glower tower. In addition to that the waste gases
separated from the Gay-Lussac tower must treat before being purged to the atmosphere.

Cooled acid steams can be obtained from the glower tower which was circulated from the
glower tower to the Gay- Lussac tower. This is the final product which has 78% concentrated

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Sulfuric acid.

An alternative mechanism and reactions for the Sulfuric production in the lead chamber had
been proposed by Lunge and Berl.

Step 1 - The Sulfur should burn to form SulfurDioxide as the starting step. The produced gas
is directed to the Glower tower.

S + O2----->SO2

Step 2 - The reaction with Nitrous fumes due to presence of H2O and NO2

NO2 + SO2 + H2O ----->HOSO2.NO(OH)

Step 3 - The oxidations of HydroxynitroSulfuric acid

2 HOSO2.NO(OH) + O-----> 2 HOSO2.NO2 + H2O

Step 4 - The Nitrosulfuric acid isomerized

2 HOSO2.NO2-----> 2 HOSO2.ONO

Step 5 - The Sulfuric acid formed by Nitrosulfuricacid and Nitrous acid is formed as a
byproduct.

HOSO2.ONO+ H2O----->HNO2+ H2SO4

Step 6 – Alternative step 5.

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2 HOSO2.ONO+ SO2 + 2H2O----->H2SO4 + 2HOSO2.NO(OH)

The mixing of gas affects the process efficiency in the lead chamber process. The
implementation of packed towers done by Gaillard-Parrish and Peterson has been considered
as a good improvement in this process.

Contact process

The equations governing the production of sulfuric acid are:

S + O2 SO2 ΔH = -70 KCal
(solid) (gas)

SO2 + 1/2 O2 SO3 ΔH = -23.50 KCal

SO3 + H2O H2SO4 ΔH = -32 Kcal

The first reaction expressing the combustion of sulfur is strongly exothermic; sulfur on
burning gives about one third of the heat of combustion of coal, and this heat raises the
temperature of combustion gases roughly in accordance with the graph as shown

This heat is high in temperature and there is plenty of it, consequently it is worth utilizing
and the hot gases are led across pipes through which the water passes. The water is heated,
steam is raised and the gases are cooled. This is the arrangement in the water tube boiler. In
the fire tube boiler the hot gases pass through the tubes which are surrounded with water.

The second equation is also exothermic and it’s apparent that the equation gives a decrease in
volume, three volumes become two volumes and this reaction would be aided by pressure.
High conversions are however, obtainable with catalysts at 400 to 500 0C with a small excess
of oxygen and the use of pressure.

The third equation represents the absorption of sulfur trioxide to form sulfuric acid. It is
exothermic and the absorbing sulfuric acid has to be cooled continuously; the heat is
available at a relatively low temperature and is not worth recovering. Sulfuric acid is used for
the absorption of sulfur trioxide as it has been found in practice that sulfur trioxide and water
form a mist, which is difficult to separate from the gas and that under these conditions the
absorption, is not complete. The strength of the acid is best about 98%.

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SULFUR HANDLING AND STORAGE:

Sulfur used for the production of sulfuric acid is practiced to handle as solid in bulk, from
ship to wagon and from wagon to cool off and solidify; it can then be broken up and
shovelled into wagons for disposal. It consists of carbonaceous matter and inorganic ash.
Although commercial sulfur is over 99% sulfur, the impurities present as dust in the plant
gases tend to be filtered out by the catalyst and a blanket or layer of hardened dust on the
catalyst detracts from the efficiency of conversion. In consequence some manufacturers filter
the molten sulfur through leaf filters to remove some of the impurities and so obtain a longer
period before the plant has to be shut down for cleaning away the dust and sieving the top
layers of the catalyst from it. However, the filter leaves have to be removed for the
replacement of the filtering medium and for the removal of the
accumulated sludge, and these unpleasant operations, together with the installation cost of the
equipment, have to be weighed against the benefits of having slightly less dusty gases.

SULFUR BURNING:

There are several types of burners for sulfur. One is revolving cylinder containing pool of
molten sulfur which is combusted by the passage of air over its surface. Another type is a
brick lined vertical cylindrical vessel in which is erected a pile of fire brick in the form of a
pyramid, and on to this structure molten sulfur is pumped to be met by a stream of concurrent
dry air for its combustion. A third variety is in the form of a burner similar to an oil burner.

The quantity of air is regulated to give between 8 to 10% SO2.

In the starting up the plant with a vertical burner the fire-brick is first heated by the burning
of a fuel gas. The gas, when a sufficiently high temperature has been reached is cut off and
the liquid sulfur is pumped over the brick-work. A measured amount of air is passed down
the burner and the sulfur burns to sulfur dioxide providing sufficient heat in normal operation
to raise the temperature of the gases to some 810-900 0C. If the air contains 21% oxygen and
sulfur is burned to give 10% sulfur dioxide gas, then 11% oxygen and 79% nitrogen will
form the residual gases. Some excess oxygen is necessary over and above that required to
combine with the sulfur and the sulfur dioxide. Out of the 11% oxygen, 5% will be required
to combine with the dioxide to form the trioxide leaving an excess of 6%. This is adequate
but if attempts were made to have a 14% sulfur dioxide gas then 14% from the 21% oxygen
would be taken up in forming sulfur dioxide and another 7% would be required to convert the
dioxide to trioxide. This would leave no excess oxygen and an excess has shown to be
essential for a good conversion of the dioxide.

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When sulfur burns, the gases rise to a temperature depending on the dioxide concentration;
with 8% sulfur dioxide the temperature is about 750 0C. To withstand these temperatures the
burner is brick lined and the area of the brickwork radiates heat and helps to burn the sulfur
completely in the time given by the volume of the burner for the passage of the gases.

The composition of the gas can be varied by altering either the air or the sulfur to the burner.
The very hot gases containing the ash from the sulfur are led straight into the waste heat
boiler.

THE WASTE HEAT BOILER:

The object of the waste heat boiler is to utilize the heat in the gases to generate steam. A
water tube boiler consists of tubes among which gases pass, the tubes being full of water. The
gases heat the tubes which in turn raise the temperature of the water. The boiler is in the form
of cylinders connected by hairpin shaped tubes arranged across the path of gases. The tubes
are kept filled with water (to prevent burning) and are connected at the top to a steam drum, a
cylindrical vessel in which water is kept at a constant level by an automatic feeding device.
The steam drum, where the water boils, is above the tubes and serves to supply water to the
boiler and for the release of steam. The surface area of the water inside the drum must be
sufficient to minimize the carryover of the spray with steam which is led off from the top of
the drum and then through super heater tubes by which the steam is heated several degrees
above its condensation temperature to give it superheat and make it free from droplets, dry
and suitable for use in turbines or other steam engines. The water circulates from the steam
drum to the sludge drum, another cylindrical shaped vessel at the bottom of the boiler, from
which the solids, deposited from the evaporating water, are sludged out and the solid content
of the boiler water controlled. The water circulates through the hairpin tubes upwards to
another cylindrical drum and then passes from this intermediate drum upwards again through
another set of hairpin tubes to the steam drum. The pressure under which steam is generated
depends upon the purpose for which it is to be employed.

There are the usual auxiliaries which are associated with a boiler, the feed pumps for
pumping the feed water into the drum against the boiler pressure, the feed water preparation
tank where phosphates and alkali are added to the water to prevent boiler corrosion, and the
economizer which heats the boiler feed water near to the temperature of the water in the
boiler drum. The feed water is sometimes preheated by exhaust steam from the boiler feed
pumps before being heated in the economizer. Preheat may be to 1000C and the final
temperature of the feed water say 2150C. The economizer and the super heater obtain their
heat from the sulfurous gases at convenient points in the process usually from the converter
after the second and third stages. Cold water in the economizer tubes could cause local

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condensation from the sulfurous gases and result in corrosion. After the first stage of
conversion there is another waste heat boiler similar in construction to the first boiler but
smaller and the two boilers use the same steam drum. The inlet gas temperature to the
converters should be 380-4000C and the waste heat boiler is designed to take away the heat
from the gases until their temperature is in this range. This reduction in temperature is about
4000C and corresponds to several tons of steam an hour form the moderate size sulfur
burning plant.

The temperature of the exit gases is controlled by a by-pass on the waste heat boiler. The
amount of heat evolved is dependent upon the quantity of sulfur and the temperature on the
proportion of sulfur dioxide in the gases. The higher the temperature, the higher is the
proportion of heat which is to be removed. It is best to gauge this so that the waste heat boiler
by-pass in normal operation is almost shut.

The waste heat boiler design takes into consideration the following factors. The area of the
tubes must be adequate to take the requisite amount of heat from the gases. This is dependent
upon the amount of heat transferred per unit of tube area, which itself is dependent upon the
velocity of gases over the tubes and the temperature difference between the gases and the
boiler water

GAS DRYING:

It has been found in practice that if moisture is present in the gases before conversion, a
sulfur trioxide mist will form after the converters, which is extremely difficult to absorb in
the acid absorbers. There are several theories to account for this. It may be that the sulfur
trioxide particles are surrounded by a film of acid and the aggregates are sufficiently small to
pass through the absorbers and out into the atmosphere, giving rise to inefficient absorption
and causing a local nuisance. There mists can be destructive to vegetation, damaging to
buildings and extremely unpleasant to life in the vicinity. It is therefore essential to use dry
air for sulfur burning or install special plant for absorbing the mist, which is a difficult
proposition.

Air is dried in a drying tower which uses strong sulfuric acid for this purpose. The tower
consists of a mild steel vertical cylinder lined with acid-resisting brick and packed with
ceramic rings. The acid is distributed down the tower and air is blown upwards
countercurrent to the acid by a blower which also serves to give the air sufficient for it to
pass through the whole of the sulfuric acid plant to atmosphere after the absorbers. The vapor
pressure of water above acids of high concentrations at ordinary temperatures can be
extremely low and consequently under the right conditions (95-98% H2SO4 at 35 0C or less)

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the acid removes nearly all the water vapor in the air that is down to 30mg/m3.

The tower has to be of a sufficient diameter not to require a significant pressure drop for the
gases to pass through it and to have an adequate surface area of packing for the absorption of
water from the air to take place in the time which the gases take to pass through the tower
volume. Consequently the gas velocity up the tower must be small, and this will determine
the minimum diameter of the tower. The amount of acid used in the tower has to be
significant to wet the surface of the packing without flooding and not to become so dilute that
its vapor pressure becomes appreciable. The amount of water in air at a given temperature
and relative humidity is known and hence the minimum quantity of 98% acid on the drying
tower can be calculated.

It is common practice to use acid from the absorption section on the drying tower; the heat of
dilution is then removed on the absorption coolers but coolers are sometimes provided on the
drying section with a bleed-off to the absorption circulation system.

GAS FILTRATION:

The gas from the burners after passage through the waste heat boiler contains ash from the
sulfur and some scale from the waste heat boiler and gas lines. These solid impurities are best
removed before the gases enter the converter; otherwise the dust accumulates on the layers of
catalyst and causes channeling through the catalyst layers, irregular contact and pressure
drop.

The filter consists simply of the wide diameter vessel filled with the filtering medium which
is commonly the lumps of quartz. The vessel is of squat cylindrical shape in mild steel. The
gases pass downwards to assist in the removal of the solids at a velocity which is slow
because of the wide diameter of the vessel. When the filter is first put into service, the
pressure drop is several m atmospheres, but when it is ready for opening and cleaning, this
pressure drop rises to some 100m atmosphere. The interval between removals of dust
depends on the ash content of the sulfur; a filter usually lasts three to six months and this
period would be extended if the molten sulfur were also filtered before burning.

In many cases the gas filtration unit may not be present and thus this step may be treated as
the auxiliary unit, depending upon the requirement. In the flow sheet given, the gas filtration
unit is not shown.

CONVERSION:

The converter is a reactor and its objective is to combine the sulfur dioxide with the residual

15
oxygen in the gases to form sulfur trioxide. The conversion is aided by a catalyst and the
more sensitive the catalyst the lower the temperature at which the conversion takes place and
more favorable the equilibrium but in general sensitive catalyst are more readily poisoned. In
practice it is necessary to have a catalyst which is sufficiently robust to resist poisoning but is
active enough to give good conversion at about 400 0C. The converter consists of a tall
cylindrical vessel of sufficient diameter (generally 3.5 to 5.5m) to give a low gas velocity,
inside which there are three or four trays for quantities of catalyst. Between the catalyst
sections there are devices for cooling the gases to keep the temperature entering the later
catalyst sections in the region of 405 to 440 0C. The first catalyst pass contain relatively little
catalyst because the reaction is rapid and the temperature rises sharply; the second a little
more, and the last stages most of the catalyst, where both the sulfur dioxide and oxygen are
less concentrated.

After the passage through the first catalyst tray when the gas temperature has risen from
about 4100C to over 6000C, the gases pass into an external waste heat boiler to raise steam
and bring the gas temperature down to 4300C and at this temperature the gases enter the
second catalyst tray. On passing through the catalyst the temperature again rises but this time
not so much, and after the second tray sufficient heat can be removed by superheating the
steam raised in the waste heat boilers. The super heater tubes are led from the boiler into a
space underneath the catalyst bed in the path of the gases. The temperature is again brought
down to about 4300C and after the third pass the gases are similarly cooled. In the final
section, which contains most of the catalyst, the temperature rise is small as the reaction has
been brought near the equilibrium value in the previous passes and only relatively small
amounts of sulfur dioxide and oxygen remain to react. After leaving the catalyst the gases are
at 400 to 4500C; they are passed through the economizer where the temperature is reduced to
a lower value. The gases then pass through an air cooler to the absorbers.

The catalyst consists of vanadium in the form of small pellets or cylinders. The total volume
is arranged to give the time of contact necessary for the reaction to take place. The speed of
the reaction depends on the activity of the catalyst. A conversion of sulfur dioxide to trioxide
of between 98 and 99 % is achieved.

The equilibrium is given by

KP = (PSO3) / (PSO2) (PO2)½

(PSO2) (PO2)½ should be as high as practicable to give a good value for (PSO3). If there is
excess of oxygen (PO2)½ will increase in value but too great an excess will diminish (PSO2)
initially. On some converters, air is introduced between the converter stages which acts as a
cooling medium and provides the additional excess of oxygen.

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Below 4000C the reaction is very slow but above 6300C the reaction is fast but the
equilibrium is becoming unfavorable, the reaction goes more quickly the higher the
temperature, but the equilibrium becomes unfavorable. The aim in running the converter is to
maintain a pattern of temperature which experience has shown will give the optimum
conversion. These temperatures depend on the catalyst activity, gas strengths and other
factors.

The running of the converter consists in close observance of temperatures, the pressure drops
and the sulfur dioxide conversion. The temperature rise across the catalyst is the measure of
the amount of reaction taking place. Pressure drops across the bed of catalyst, if they are
abnormally high, indicate a partial blockage and channeling through the catalyst, which
would be accompanied by a small temperature rise. A high pressure drop across the first pass
may necessitate shutting down the plant and screening the top layer of the catalyst which has
possibly become choked with dust.

ABSORPTION:

The gas leaving the reactor is cooled further in a heat exchanger as mentioned above and
before entering the absorption tower where the Sulfur trioxide is absorbed in a recirculated
stream of concentrated sulfuric acid. The sulfuric acid is maintained at desired concentration
(usually 98% H2SO4) by the addition of water and its temperature is controlled in the desired
range of 70 to 900C measured at the tower inlet by cooling the recirculated acid.

Some of the acid goes to the air drying tower mentioned previously where the moisture from
the incoming air supplies some of the water needed in the reaction. Since, the heat released in
this step is at a low temperature level, little use can be made of it. In the above mentioned
Single Absorption process, the recovery of the sulfur as sulfuric acid is 97-98% and the
remainder is lost to the atmosphere as Sulfur dioxide. In many countries, the discharge of this
amount of Sulfur dioxide to the atmosphere is environmentally unacceptable. Therefore most
of the plants use a Double Contact Double Absorption Process (DCDA)

The gas after passing through three catalyst bed goes to the first absorption tower where the
Sulfur trioxide is removed. The gas is then reheated to about 4200C, passed through the
fourth catalyst bed, then cooled and sent to a second absorption tower.

In the reaction
2SO2 + O2 2SO3

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 removal of the reaction product sulfur trioxide facilitates more efficient conversion in the last
catalyst bed. The DCDA process reduces the sulfur dioxide loss to less than 2Kg of sulfur
dioxide/ ton of the sulfuric acid. High efficiency mist eliminators are also required to limit
the loss of sulfuric acid mist to less than 0.05Kg/ton of sulfuric acid. Thus the recovery in a
DCDA plant should atleast be 99.8%.

THE TAIL GAS:

The gas from the absorption section contains about 0.15 % sulfur dioxide which oxidizes in
part to sulfur trioxide and forms mist. At this concentration, corresponding to a conversion
efficiency of over 98%, the effluent is tolerable and no further treatment of gas is required. In
exceptional cases where the oxygen content is low or for other reasons where the conversion
is down, the gases can be scrubbed with ammonia liquor and then treated by electrostatic
precipitator.

STORAGE:

The last part of the sulfuric acid plant is the storage and the pumping system. The tanks are
large flat cylinders which are sometimes of more than 100 tons capacity. The pumping of
acid is commonly done by the centrifugal pumps, the submerged glandless type on smaller
tanks where the shaft can be less than about 10ft in length. The absence of gland leaks makes
for a neat and clean pumping section. The storage installation should be calculated to
maintain continuity of supply, if this is required, during the shutdowns of the acid plant and
to cater for peak demands.

PROCESS SELECTION
Comparison between the Lead Chamber Process and the Contact Process

Economic aspects- Product quality and concentration: It was indicated that the concentration of
the final product from the contact process is about 98% Sulfuric acid. Recall also that the output
concentration of the final product in Lead Chamber Process is more dilute acid content of 62%-
78%. The reason for this difference can be attributed to the Catalytic activity of V2O5 which
delivers an impressive 99.5% conversion in the catalytic converter in the contact process. Of
course it should be borne in mind that regardless of the quality achieved within the process,
impurities in raw materials will affect the ultimate purity. Major disadvantages in the Lead
Chamber process in terms of productivity thus include the limitations in throughput, quality and
concentration of the acid produced with respect to the Contact Process.Currently most end uses
of Sulfuric acid are for the high concentrated form. Thus in terms of product capacity and
concentration, the contact process is a more attractive option.

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Operating cost: The operating cost as the name implies is driven by the requirements that are
unique to the process. In chemical processes operating pressure and temperature occupies a
significant portion of this. For the contact process it is stared that high pressures favour the
forward reaction in the catalytic converter (i.e. SO3). However, larger pressures and
temperatures automatically increase the plant operating cost. Fortunately however, this high
pressure requirement only amounts to 1-2 atm in the contact process where it is sufficient to
achieve the desire 99.5% conversion. In other words, at pressures only slightly above the
atmospheric, the marginal pressure rise is sufficient to obtain the target yield, and since the
operating pressure requirement is not abnormally high, cost of equipment are lower than what
could have been expected.

Energy consumption: Energy consumption for Sulfur burning is same for the two process
because in our case elemental sulfur will be procured to produce sulfur dioxide. In the old lead
chamber process however, there are other reactions to produce nitrogen oxides. So it could be
generally stated that the lead chamber process require more energy for burning of KNO3. The
burning step is in any case, the main energy consuming step. In the modern lead chamber
process, SO2is sent to the glower tower. That means the initial step of the both processes is
same. In addition to thisthough, in the lead chamber process 3 to 12 lead chambers are operated
as convertors which overall consume higher energy amount to provide and circulate the gases
and other liquid acids for the lead chambers. In the contact process there is a specific column as
converter and even in the case of the double contact double absorption contact process, only few
additional gas conveying lines are needed. The contact process therefore consumes less energy
amount in terms of gas and liquid circulation utilities of the plant. This advantage is due to the
fact that the contact process is compact and less of gas circulation needs than the lead chamber
process and this matter because more gas conveying require more pumps and air blowers As far
as heat emission and heat recovery systems are concerned, the two main processes are mostly
equal owing to the following reasons: • Contact process- Sulfur burning step need over 1000oC
and the catalytic conversion step needs 450oCto operate in the optimum range. The catalytic
conversion step and absorption step both generate heat. It follows that this heat could be
recovered. The high temperature involved certainly makes the heat high ‘quality’ heat; the exact
quantities could be established after conducting a pinch analysis.

• Lead Chamber Process- The temperature requirement in KNO3 and S burning exceed 1000oC
and that heat requirement might be more than the contact process requirement. In fairness
however, modern lead chamber process also send SO2 to the glower tower which can balance
out the energy consumption.

Safety aspects Production of Sulfur Dioxide is a key step in both processes. Fugitive emissions
amounting to impressible levels or process hazards resulting in major leaks of SO2would
compromise the health of factory personnel and even beyond. The environmental impact of
oxides of Sulfur are thus common in both cases. In addition however, the lead chamber process

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involves production of oxides of Nitrogen as catalysts for the reactions where Burning of Niter
leads to production of NO. This is subject to oxidation by Oxygen.

2 NO + O2 → 2 NO2

With presence of water this nitrogen dioxide can convert to the nitrous acid and nitric acid.

2 NO2 + H2O → HNO2 + HNO3

These two acids have a considerable risk factor where they may be emitted to the environment
through pipes and 3 main towers in the lead chamber process. These reactions also form part of
the lead chamber process reactions in the lead chambers. The contact process therefore has a
relatively lower impact on the environment.

Process selection

Engineering design require emphasis on risk reduction in terms of safety and wellbeing of
personnel, society and the ecosystem. Optimum process selection for Sulfuric acid should
incorporate process and economic realities with minimum risk and minimum foot print on the
environment. Considering the above comparison of the two processes the contact process have
more advantages in terms of its relative advantages in terms of operations economics, energy and
safety issues Considering above factors, the Contact Process will be selected. A complete
process selection, however require identification of the minor variations within the contact
process.

There are 3 main processes that come under the contact process.

● Single contact single absorption process(SCSA)

● Double contact double absorption process(DCDA)

● Wet Contact Process (WCP)-This is not widely used in large scale due to sulfuric acid mist
generation in the absorption of the SO3 to H2O directly.

Production process

Thus process selected is the contact process with the double contact and double adsorption
system.

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Conclusion

The plant design of sulfuric acid plant involves the different process and system maintaining
techniques with the environmental aspects too. The flow sheet of manufacture of sulphuric acid
by contact process is read and understood by the students. The material balance and the process
calculation along with all the concept has been done by student. They are able to understand the
chemical process calculation.

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