Complete Project

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Chapter 1
Introduction
Sulphuric acid is one of the most important chemical having a wide variety of industrial
usage. Sulphuric acid is the oldest chemical product and is the largest-volume chemical
manufactured in the world. Its consumption is often cited as an indicator of the general state of a
nation's economy, and although many other indicators (such as energy consumption) might today
be regarded as more important, sulphuric acid consumption still follows general economic trends.
It is a strong mineral acid with the molecular formula H 2SO4. It is one of the heavy chemical as it
is most widely used and most important technical product. It is a dibasic acid and acts as a
dehydrating and oxidizing agent. It is a strong acid and reacts with most of the metals either the
dilute or concentrated form. The concentrated acid is a strong oxidizing agent, especially at
elevated temperatures. It is an agent for sulphonation and sulphate formation but most frequently
it is used because it is a rather strong and most cheaply priced inorganic acid.
Sulphuric acid is one of the most-used commodities in the world, with global consumption of
more than 200m tones/year. Trade is limited to around 15m tones/year because acid is consumed
at the site where it is produced, in addition to domestic demand within key markets being strong.
Europe, South Korea and Japan are the top three exporters of sulfuric acid, while China, Chile,
and the Asia-Pacific region, including Australia and India, are the top three geographies for
imports. The production and consumption pattern of sulphuric acid is shown in the following
diagrams:
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Production Consumption
Fig 1.1: World Sulphuric Acid Production and Consumption in 2007 (Source:
www.outotec.com/38365.epibrw)
About 65% of the world’s sulphuric acid production was based on elemental sulfur, 16% of
pyrite and 19% of other sources. There are so many uses of sulphuric acid that any detailed
listing is likely to be incomplete or include aggregate categories. A common description of
sulphuric acid demand according to the primary uses is shown in the following figure:
Fig 1.2: Global Sulphuric Acid Demand by Application (Source:

www.chemsystems.com/reports/search/docs/toc/0708S8)
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Chapter 2
Properties and Uses of Sulphuric Acid
2.1 Physical Properties Of Sulphuric Acid
Sulphuric acid, also spelled as Sulfuric acid, is called Oil Of Vitriol, or Hydrogen Sulphate acid,
is a dense, colorless, oily, corrosive liquid. When heated, the pure acid partially decomposes into
water and sulfur trioxide. It is soluble in all proportions in water. Sulfuric acid is a very strong
acid in aqueous solution; it is changed to hydrogen ions (H +) and sulfate ions (SO42-). Aqueous
sulphuric acid solutions are defined by their H2SO4 content in weight % terms. Anhydrous
(100%) sulphuric acid is referred to as monohydrate of sulfur trioxide. Sulphuric acid will
dissolve any quantity of sulfur trioxide SO3 forming oleum. The concentration of oleum is
expressed in weight % of dissolved SO3 (free SO3) in 100% H2SO4 .The general physical
properties of sulphuric acid are tabulated:
Color Colorless , water-white

Empirical Formula H2SO4
Molecular Weight 98.08
Melting Point 10.4o C
Boiling Point 340 o C (Decomposition)
Specific Heat 1.4435 KJ/Kg
Specific Gravity 1.8357
Heat Of Dilution 9.304 KJ/Kg Water
Solubility In Water Miscible , liberates much heat
Corrosion Highly corrosive on metals, stone.
Polarity Very polar
Conductivity High electrical conductivity
Viscosity 26.7 Cp(20oC)
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Standard Enthalpy Of Formation -8.305KJ/ Kg

pH 0.3, 1.0, 2.1 @49 g/L
pK pK1: -3; pk2: 1.92 @ 25ºC
Table 2.1 Physical Properties of H2SO4
Sulphuric acid is not a one-quality product. It is produced and supplied in exact purity for storage
batteries, rayon, textiles, dyes, food and pharmaceutical industries, in less pure grade for steel,
heavy chemicals, petrochemicals, fertilizers, super phosphates and ammonium sulphate
industries.
Sulphuric acid is used in wide range of concentrations from very dilute for pH control to the
strong fuming acids used in dyes, explosives, detergents, pharmaceuticals and petrochemical
industries.
Standard strengths available in the market are listed below:-
SPECIFIC GRAVITY -1.250 33.33%

SPECIFIC GRAVITY- 1.400 50.08%
SPECIFIC GRAVITY- 1.500 59.80%
SPECIFIC GRAVITY -1.550 93.19%
60˚ BAUME 77.67%
66˚BAUME 93.19%
20% OLEUM 104.5%
40% OLEUM 109.0%
Table: 2.2 Standard Strengths of H2SO4
2.2 Chemical Properties of Sulphuric Acid
 Sulphuric acid is a diprotic acid (can donate 2 protons to a base)
 Sulphuric acid ionizes in water in two stages:

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H2SO4(l) + H2O(l) HSO4-(aq) + H3O+(aq)
HSO4-(aq) + H2O(l) SO42-(aq) + H3O+(aq)
 Sulphuric acid is a strong acid (complete dissociation in water, Ka approaches infinity)
 Sulphuric acid reactions:
 sulphuric acid + metal metal sulfate + hydrogen gas
 sulphuric acid + carbonate metal sulfate + carbon dioxide gas + water
 sulphuric acid + base salt + water
 sulphuric acid + ammonia ammonium sulfate
 Sulphuric acid can take part in redox reactions.
2.3 Applications of Sulphuric Acid
1. Sulphuric acid is an active acid with a high boiling point. The manufacture of halogen acids
namely HCl, HF etc and pickling of steel make use this high boiling point.
2. Sulphuric acid has great affinity for water. It is widely used for drying gases containing
moisture (e.g.-Cell Chlorine). Virtually complete removal of water vapour from these gases is
accomplished by simple scrubbing operation.
3. Sulphuric acid forms hydrolysable sulphates 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 alkyl amines important to dye,
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photographic and pharmaceutical industries are manufactured with sulphuric acid. The
production of industrially important synthetic alcohols is also based on this sulphuric acid
property.
4. Sulphuric 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 and lubricants.
7. Sulphuric 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
Sulphuric 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 sulphuric acid. Large amounts of sulphuric 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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Chapter 3
Review of Literature
3.1 A Brief History
The actual discovery of sulfuric acid dates back to the era of the alchemists (864-930 A.D).
European scientists apparently did not discover sulfuric acid on their own until the sixteenth
century, when the Belgian scientist Johann Baptista van Helmont (1579–1644) described its
preparation by adding water to the gas formed when sulfur was burned. Sulfuric acid was called
"oil of vitriol" by medieval European chemists. In the 17th century, the German-Dutch chemist
Johann Glauber prepared sulfuric acid by burning sulfur together with saltpetre (potassium
nitrate, KNO3), in the presence of steam. As saltpeter decomposes, it oxidizes the sulfur to SO3,
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which combines with water to produce sulfuric acid. The discovery of sulfuric acid proved to be
an important development in the early history of modern chemistry.
3.2 Commercial Methods of Preparation
1. Lead Chamber Process: The first commercially successful method for making sulfuric acid
was developed in 1746 by English physician, chemist, and inventor John Roebuck (1718–1794).
Roebuck's method is called the lead chamber process because the acid is made in large
containers lined with lead. Sulfur dioxide is introduced along with steam and oxides of nitrogen
into large chambers lined with sheet lead where the gases are sprayed down with water and
chamber acid. The sulfur dioxide and nitrogen dioxide dissolve and over a period of
approximately 30 minutes and the sulfur dioxide oxidized to sulfuric acid. The presence of
nitrogen dioxide is necessary for the reaction to proceed. The process is highly exothermic, and a
major consideration of the design of the chambers was to provide a way to dissipate the heat
formed in the reactions. This process was improved when Clement and Desormes introduced
supplemental air into the lead chambers, thereby increasing the efficiency. In the mid 19th
century, French chemist Gay-Lussac redesigned the chambers as stoneware packed masonry
cylinders, which in absorbing nitrogen oxides from lead chamber off-gases. In the 20th century,
plants using externally cooled Mills-Packard chambers supplemented the earlier designs.
However a fundamental disadvantage of this process is that the product concentration is limited
to a maximum of 70-75%. This process is practically obsolete now.
2. Contact Process: It was invented about 1830 by an English vinegar merchant from Bristol,
Peregrine Phillips. This process involves the oxidation of sulfur dioxide to sulfur trioxide over
finely divided platinum catalyst at high temperature. Phillips found that the yield obtained (the
amount of raw material converted to useful product) was much higher than with the lead
chamber process. The contact process have evolved a lot from its inception and today it is the
universally used method. The first improvement came around 1930 when platinum was replaced
by vanadium pentoxide because of its insensitivity to catalysts poisons and its lower costs. In
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1936-37, Lurgi introduced the wet contact process for converting moist sulfur dioxide containing
gases over a vanadium catalyst. This made it possible to process hot gases from the combustion
of hydrogen sulphide in coking plants directly to sulfuric acid. In succeeding years, the raw
material basis of the industry changed progressively from mainly roaster gases to sulfur
combustion gases containing higher concentrations of sulfur dioxide. In 1960, Bayer patented the
so-called double-catalysis process where he incorporated a preliminary SO 3 absorption step
ahead of the final catalytic changes. This improved contact process permitted a decisive increase
in overall SO2 conversions, thus reducing SO2 emissions substantially. This process is more
commonly referred as the “double-absorption” process.
Chapter 4
Brief Description of DCDA Process
4.1 Raw Materials and Products
The starting material for sulphuric acid manufacture is clean, dry SO 2, 8 to 12% in O2, N2, SO2,
CO2, SO3 gas. It is obtained:
 By burning molten waste elemental sulphur (~70% of world production)
 From high SO2 strength metallurgical off-gases (~20%)
 By decomposing spent (used) sulphuric acid catalyst (~10%).

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The first and last process beneficially make a useful product from waste. The second process
beneficially removes SO2 from smelting and roasting off-gases.
The product of sulphuric acid manufacture is liquid acid, 93 to 98% H2SO4, 2 to7% H2O.
4.2 Manufacturing Process
Sulphuric acid manufacturing consists of the following steps:
1. Gas cleaning and gas drying
2. Generation of sulphur dioxide
3. Catalytic oxidation of sulphur dioxide to sulphur trioxide
4. Absorption of sulphur trioxide
5.Acid Cooling
1. Gas Cleaning and Gas Drying
The gas entering dehydration must be dust free (0.001 to 0.01 g/Nm3 of gas) to avoid plugging
downstream SO2-oxidation catalyst. Dust is removed from the gas by a series of electrostatic
precipitation and scrubbing steps. Metallurgical off-gas requires the most attention. Sulphur
burning requires the least. Gas drying is an important process in contact plants. Acid plants must
be built and operated so that liquid sulphuric acid is not produced in unexpected locations in
equipment and flues. Gas drying protects cooler parts of the plant, such as heat exchanger,
against corrosion by acid condensation, and it safeguards against the formation of sulphuric acid
mist, which can be very difficult to absorb. It protects the catalyst from ill effects of acid
condensation when the plant is shut down for any reason. Therefore, both the operating
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performance (especially tail gas purity) and the service life of the plant depend in large measure
on an efficient and reliable gas drying stage. In sulphur-burning plants the molten sulphur used is
dry from the outset, because its melting point is well above the boiling point of water, and any
moisture originally present will have been driven off in the melter. The combustion air, however,
must be dried. In the usual arrangement, filtered air from the atmosphere is drawn through a
drying tower by the main blower.The drying tower uses strong sulfuric acid as the dehydrating
agent. 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 35oC or less) the acid removes nearly
all the water vapor in the air that is down to 30mg/m3.
2. Generation of Sulphur dioxide
For a sulphur burning plant, sulphur is converted to sulfur dioxide by burning molten sulfur with
dried air in a sulfur burner to yield a 1000-1200°C gas stream containing 10-12 percent S0 2. The
reaction involved is:
S (l) + O2 (g) SO2 (g) ΔH= -298 kJ/mole,25˚C
The burner is mounted at one end of a sulfur furnace, and the gas passed through a waste heat
boiler at the other end. The gas temperature is reduced to 420-440°C on leaving the boiler, which
produces steam. In the simple pressure-nozzle burner, the liquid sulfur is atomized by pumping
through the nozzle. In a two component burner, the sulfur is atomized primarily by the
combustion air stream. It operates at lower pressure and has a wider sulfur throughput range, 5-
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170 tons/day, than the simple burner. Lurgi's rotary burner can burn up to 400 tons/day of sulfur.
Larger sulfuric acid plants use multiple sulfur guns in a single furnace to bum 1400 metric tons
per day of sulfur. A process gas with 18 percent S0 2 can be achieved in Lurgi's two-stage sulfur
combustion process. However, S02 gas produced from burning sulfur in air at 18 percent cannot
be used directly in a contact sulfuric acid plant without the addition of dilution air as there is not
enough oxygen in the gas stream to react with the S02 to achieve a normal conversion to SO3. In
the two-stage process excess sulfur is burned in the first stage, consuming all of the oxygen. The
low residual oxygen level limits the formation of nitrogen oxides, which otherwise would be
very high at the combustion temperature of 1100°C. The combustion gas then is cooled to 620-
650°C, and additional dried air is injected to burn the residual sulfur in an afterburner. A second
waste heat boiler cools the process gas to 420-440°C before sending it to the converter.
3. Catalytic Oxidation of Sulphur dioxide to Sulphur trioxide
Oxidation of S02 to S03 is accomplished in multi-stage, fixed-bed catalytic converters equipped
with interstage boilers or heat exchangers to remove the heat of reaction. The reaction that takes
place is:
catalyst
SO2 (g) + ½ O2 (g) SO3 (g) ΔH= -98.3 kJ/mole,25˚C
Typically, four stages are compartmented within a single vertical converter, which may be brick-
lined, steel, or cast iron. Newer converters are stainless steel, and some have five stages for
higher conversion. Isothermal tubular converters are no longer suited to modem high-capacity
plants. The extruded cylindrical catalyst pellets are usually 4-9 percent V 205 with alkali metal
sulfate promoters on a silica carrier (diatomaceous earth, silica gel, or zeolites). The reaction
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temperature for vanadium catalyst is generally 410--440°C. In the late 1980s a cesium-promoted
catalyst became commercially available from Topsoe and Monsanto. These low-strike catalysts
operate at 360--400°C.Higher temperatures (~600°C) reduce the SOz conversion and lead to
structural damage of the catalyst. High-pressure drops across catalyst beds from catalyst dust
formed during processing require periodic catalyst removal and screening to remove dust. Ring-
shaped catalysts developed by Topsoe and others have lower dust pressure drops and are now in
wide use. Other catalyst shapes used are ribbed rings and cylinders. The usual catalyst loading
per one ton/ day sulfuric acid capacity is 150-200 L in a double absorption plant.
Fig 4.1: Photograph of catalyst pieces, courtesy Haldor Topsøe A/S

Source: http://www.haldortopsøe.com
4. Absorption of Sulphur trioxide
In principle, H2SO4(l) can be made by reacting the SO3(g) from catalytic oxidation with water.
The reaction is:
SO3 (g) + H20 (l) H2SO4 (l) ΔH= -130 kJ/mole,25˚C
However, the reaction is so exothermic that the product of reacting strong SO3 with water would
be hot H2SO4 vapour. Condensation of H2SO4(l) from this vapour is slow and expensive, so the
SO3-water process is not used for strong gas. Instead, the SO3(g) is reacted with the H2O(l) in
strong sulphuric acid. The small amount of H2O and the massive amount of H2SO4 in the reaction
input acid avoids this problem. The small amount of H2O limits the extent of the reaction. The
large amount of H2SO4 absorbs heat of reaction.

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Sulfur trioxide from the converter is absorbed in 98 percent H 2S04 recirculated counter currently
through a packed tower maintained at 60-80°C by indirect cooling. The optimum concentration
of the absorber acid is near the H 2O-H2S04 azeotrope, 98.3 percent H2S04, where the S03, H2S04,
and H2Ovapor pressures are at their lowest values. Absorption efficiencies in excess of 99.9
percent generally are obtained. On leaving the converter, the process gas is cooled first with feed
gas in a gas-gas heat exchanger and then with boiler water in an economizer to 180-220°C before
it enters the absorber. An impingement separator, or Teflon or glass fiber mist eliminator, is
placed in the top of the absorber to remove acid mists. If oleum is produced at the plant, it is
made in a separate oleum tower upstream of the absorber. A portion of the S0 3 stream to the
absorber is diverted to the oleum tower where it is absorbed in a recirculating stream of oleum.
In double absorption plants an intermediate absorber is placed between the second and third (or
between the third and fourth) converter beds. By removing S0 3 from the gas stream at this
intermediate point, higher SO2conversions are attained in the downstream converter beds, and
the overall SO2 conversion is increased. The cooled gas from the intermediate absorber is
reheated by hot converter gas in gas-gas heat exchangers before returning to the converter. An
oleum tower may be placed before the intermediate absorber.
6. Acid Cooling
Absorption of S03 in concentrated sulphuric acid and the formation of H2SO4 from SO3 and H2O
produce heat in the absorber, as does acid dilution from the addition of makeup water. Process
control requires that the acid be cooled before it is recirculated to the dryer or absorber towers or
sent to storage. Earlier acid coolers of parallel banks of stacked, irrigated, cast iron sections have
been largely replaced by stainless steel shell and tube or plate exchangers, with or without anodic
protection. Hastelloy, Sandvik SX, ZeCor, and Saramet alloys and Teflon linings are also
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used in acid piping and coolers.
Chapter 5
Kinetics and Thermodynamics of the Process
5.1 Reaction kinetics and Thermodynamics
SO2 is oxidized to SO3 in preparation for H2SO4 making. The oxidation is done by blowing clean
dry SO2 gas down through horizontal beds catalyst.
1 catalyst
SO2 + /2 O2 SO3 ΔH= -99 kJ/mole
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This is reaction is a reversible reaction. A reversible reaction is a reaction where the forward and
reverse reaction proceed continually at the same time. Initially, the forward reaction rate is high
producing SO3. As the quantity of SO 3 produced increases, the rate of the reverse reaction begins
to increase while the rate of the forward reaction decreases. When the rate of the forward and
reverse reaction is the same, the reaction has reached a state of equilibrium. At equilibrium the
concentration of reactants and products does not change. The position of equilibrium in the gas-
phase exothermic oxidation of sulphur dioxide to sulphur trioxide depends on the prevailing
temperature, total pressure, and concentrations (partial pressures) of the reactants.
Thermodynamic equilibrium is determined by the equilibrium constant Kp. According to the law
of mass action
Pso3
Kp =
Pso2 ˟ Po2 1/2
On account of the negative reaction enthalpy of sulphur dioxide oxidation, both Kp and the SO2
equilibrium conversion decrease with rising temperature. The classical relationship between Kp
and temperature was developed empirically by Bodenstein and Pohl.
The relation is given as
5186.5
logKp = T + 0.611 logT – 6.75 ,T is in K
Solving the two equations together generates the equilibrium curve. Many different equilibrium
equations have been proposed by researchers to describe observed experimental results and
behaviour. Some of the variables that define the equilibrium equation are SO2 and O2
concentration (i.e. high vs. low), operating temperature and catalyst types.
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5.2 Equlibrium Response due to Change in Temperature
Fig 5.1: Equilibrium conversion as a function of temperature
It shows that the reaction goes almost to completion at 400˚C but not at 750˚C.This indicates that
raising reaction temperature to increase reaction rate is counter-acted by a large decrease in ma-
-ximum attainable (equilibrium) SO3 production. This problem is overcome by using catalyst,
which promotes rapid SO2 oxidation at cool temperatures (~400˚C) where equilibrium SO 3
production is efficient. The catalyst is molten V, K, Na, Cs, S, O solution on porous silica
substrate. A simplified reaction scheme with this catalyst is:
SO2 + 2V5+ + O2 2V4+ + SO3 …………………….(a)
½ O2 + 2V4+ 2V5+ + O2- ……………………...(b)
which combine to give:
SO2 + ½ O2 SO3 ………………………………......(c)

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Reactions (a) and (b) have lower activation energies than reaction (c), giving rapid reaction at
400-700 ˚C.
5.3 Shift in equilibrium curve with change in SO2 concentration
Fig 5.2 Equlibrium conversion for different feed concentration
The equilibrium curve will shift upwards when the base SO2 concentration is lower. That is why
higher overall conversion can be obtained when SO 2 concentrations are lower. Unfortunately,
diluting the gas to lower SO2 concentration results in large gas flows and a larger more expensive
plant. Industry trends are to operate at higher SO 2 concentrations to reduce gas flow and plant
size.This shift in the equilibrium curve is important for double absorption plants.
5.4 Le Chatelier’s Principle and Its Application for Output Maximisation
According to Le Chatelier’s principle:

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“Any change in one of the variables that determines the state of a system in equilibrium causes a
shift in the position of equilibrium in a direction that tends to counteract the change in the
variable under consideration.”
Simply put, Le Chatelier's Principle states that a system in equilibrium responds to any stress by
restoring the equilibrium. The reaction of sulphur dioxide with oxygen to form sulphur trioxide
follows the principles outlined by Le Chatelier.
1 catalyst
SO2 + /2 O2 SO3 , ΔH= -99 kJ/mole
1. Effect of temperature: Because heat is generated in the reaction, removing heat will result in
more SO3 formation.
2. Effect of pressure: SO2 and O2 represent 1½ volumes of reactants while SO3 is only 1 volume.
Therefore increasing the pressure at which the reaction occurs will result in more SO3 formation.
3. Effect of concentration: Removing reaction products will result in the formation of more
products.
However these are purely thermodynamic conditions, which only relate to an yield. In an
industrial process, the rate of reaction is also important.
5.5 Compromise Reaction
After thorough analyzing of the rate and equilibrium conditions, industrial chemists have decided
on compromise conditions for this step of the contact process. The final reaction conditions are:
1. Reaction is carried out stage-wise in multiple beds with cooling in between catalyst beds,
utilizing the principle of removing heat (i.e. lower temperature) to achieve higher overall
conversions. This is the same principle used in an ‘isothermal’ converter. A moderate
temperature ranging from 400-550˚C is maintained.

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2. Catalyst of vanadium pentoxide is used to promote the reaction at low temperature.
2. A pressure of a little higher than atmospheric pressure is used. Increased pressure will even
though increase the yield, but high pressure equipment is expensive and dangerous to build and
maintain.
3. The removal of SO3 from the gas mixture to promote higher overall conversions is the main
principle behind the double absorption plant where intermediate absorption of SO2 is done.
5.6. Reaction Path of DCDA Process and Its Advantages
The reaction path of DCDA process in comparison with that of Single absorption plant is shown
in the following figure:

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SO2 conversion
Temperature in ˚C
Fig 5.3: Comparison of reaction profiles
The figure shows the reaction profile for a converter comprising four beds and operating under
adiabatic conditions, together with the SO2 conversion attainable in each bed within the general
limits of actual conversion characteristics. A profile for the normal contact process without
intermediate absorption (single absorption) is compared with that for a double absorption process
with intermediate absorption after the third bed . It is evident that the overall conversion
ultimately obtained in the double absorption process is substantially greater than in a single
absorption process with the same number of catalyst beds. In a single absorption plant the max-
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-imum achievable conversion with a typical four bed converter is 97.8% which contrasts with a
final conversion >99.5% in the double absorption plant.
Advantages of the DCDA process:
 High SO2 conversion 99.9% can be obtained.
 Feed gas with a higher sulphur dioxide concentration can be processed.
 Extent of SO2 emission to stack is negligible and hence the pollution is less.
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Chapter 6
Initial Material Balance
Assumptions
1) Complete burning of S in the burner.

2) 99.8% conversion of SO2 to SO3 in the reactor.
3) Overall absorption of SO3 in the process 100%.
4) 40% excess oxygen is provided.
5) Humidity of entering air is 70% at 30°C.
Basis: 100 k mol/hr of elemental Sulphur.
Assuming 100% conversion of Sulphur to SO2
S + O2 SO2
1
SO2 + O SO3
2 2
Total SO2 provided = 100 k mol
Total O2 required = 150 k mol
Some Oxygen must be taken in excess:
Assuming 40% Excess O2,
Total O2 required= 150 x 1.4 = 210 k mol
Dry air coming in = (210 x 100)/21 = 1000 k mol = 29000kg (molar mass of air = 29)
Assuming, at 25oC and 70% relative humidity from psychometric chart = 0.0189kg water/kg dry
air
Therefore, water entering with dry air = 0.0189 x 29000 = 548.1kg = 30.45 k mol
Total wet air entering = 30.45 + 1000 = 1030.45 =1030.45 k mol

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6.1: Drying Tower:
Q (Dry air) 1000 k mol
R (98%H2SO4 for
Dryer)
P (wet Air)
1030.45 k mol
S (Wet 97%H2SO4 after absorbing moisture)
Fig: 6.1 Drying Tower
Assumption:-
1) All the water vapour is completely removed from wet air.

2) The concentration of 98% recycled acid decreases to 97%.
Calculation:
Overall material balance:
P + R= Q + S
As water is being removed from the incoming air to make it dry, the 98% acid being recycled
decreases in concentration to say 97%
Making a balance for H2O:

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548.1 + 0.02R= 0.03S
0.02R–0.03S = - 548.1 --------------------- (1)
Making a balance for H2SO4,
0.98R = 0.97S
0.98R-0.97S=0 ---------------------- (2)
Solving (1) & (2) we get R=53165.7 Kg S=53713.8 Kg
Materials In Materials Out

Component K mol Kg Component K mol Kg
Wet Air 1030.45 29548.1 Dry Air 1000 29000
Dry H2SO4 531.657+59.073 53165.7 Wet H2SO4 531.657+89.52 53713.8
3
Total 1621. 82713.8 Total 1621.8 82713.8
Table: 6.1 Material Balance of Drying Tower
6.2 Sulphur Burner
Sulphur (100 K mol)
Dry Air (1000 k mol) SO2
Fig: 6.2 Sulphur Burner
The Combustion takes place inside the burner where Sulphur is oxidized to Sulphur Dioxide
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Moles of Sulphur coming in = 100 k mol = 3200 kg
Moles of O2 coming in = 210 k mol = 6720 kg
Assuming 100% conversion of Sulphur (S) to (SO2)
S + O2 SO2
SO2 formed= 100 k mol = 6400 Kg
O2 leaving = 210-100=110 k mol = 3520 kg
N2 coming in and going out (unchanged) = (79 x 210)/21 = 790 K mol = 22120 kg

S 100 3200 SO2 100 6400
O2 210 6720 O2 110 3520
N2 790 22120 N2 790 22120
Total 1100 32040 Total 1000 32040
Table: 6.2 Material Balance of Sulphur Burner

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6.3: Monsanto four stage Reactor
Outlet1
Inlet 2
Outlet 2
Inlet 3
Outlet 3
Inlet 4
Outlet 4
Fig: 6.3 Monsanto Four Stage Reactor
As cited in the reference by author Norman Shreve the conversion in each stage of Monsanto
converter is given as follows:-
Stage % conversion
1 74.0
2 18.4
3 4.3
4 3.1
Overall conversion 99.8
Table: 6.3.1 Conversion in the reactor (4 stage catalytic converter).
Conversion of SO2 to SO3 takes place according to following reaction.

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SO2 + 1/2 O2 SO3
In The First Bed Of Catalyst 74% Conversion Is Attained:
SO3 formed = 0.74 x 100 =74 k mol.

SO2 remained = 100 – 74 = 26 k mol.
O2 remained =110 – (1/2 x 74) = 73 k mol
N2 remained = 790 K mol.
SO3 74 5920
SO2 100 6400 SO2 26 1664
O2 110 3520 O2 73 2336
N2 790 22120 N2 790 22120
Total 1000 32040 Total 963 32040
Table: 6.3.2 Material Balance for 1st bed in the reactor.
In The Second Bed of Catalyst 18.4% Conversions Attained:-
SO3 formed = 0.184 x 100 = 18.4 K mol.
SO2 remained = 26 – (01.84 x 100) =7.6 k mol.
O2 remained = 73 – (0.184x100/2) = 63.8 K mol.

SO3 74 5920 SO3 92.4 7392
28
SO2 26 1664 SO2 7.6 486.4

O2 73 2336 O2 63.8 2041.6
N2 790 22120 N2 790 22120
Total 963 32040 Total 953.8 32040
Table: 6.3.3 Material Balance for 2nd bed in the reactor.
In The Third Bed of Catalyst 4.3% Conversion Is Attained:-
SO3 formed = 0.43 x 100= 4.3 K mol.
SO2 remained =7.6 – (0.43 x 100 ) = 3.3 K mol.
O2 remained = 63.8 – (0.43 x 100) =61.65 K mol.

SO3 7.6 486.4 SO3 96.7 7736
SO2 92.4 7392 SO2 3.3 211.2
O2 63.8 2041.6 O2 61.65 1972.8
N2 790 22120 N2 790 22120
Total 953.8 32040 Total 951.65 32040
Table: 6.3.4 Material Balance for 3rd bed in the reactor.
6.4 First Absorber:-
(SO3=40.458k mol
SO2=3.3k mol
29
O2=61.65k mol
N2=790k mol)
98% H2SO4
Inlet from 3rd stage converter
(SO3=96.7k mol
SO2= 3.3k mol
100% H2SO4
O2 =61.65k mol
N2=790k mol
Fig: 6.4 First Acid Absorber
After the passage through the 1st stage or after the 1st contact, the gases are let in the 1st absorber
where the absorption of SO3 takes place. After that the gases are returned back to the 4th stage of
the converter for 2nd contact:-
According to the reaction
1
SO2 + O ⇌ SO3
2 2
( PS O3)
Kp =
(PS O2) ¿ ¿
Rewriting the expression for Kp in terms of mole Fractions and total pressure for the equation-
2SO2 + O2 2SO3, we get
N x n2 S O3
Kp = 2
n S O3 x n O2 x P
Where,
n = Number of moles of each component.
N= Total moles.
P = total pressure.
30
By rearranging, we get.
2 n2 S O 2 x n O 2 x K p x P
n SO3 =
N
Assumptions:-
After absorption the remaining gases enters the fourth stage at 427°C, K p =257 is taken from
Dryden.
3.32 x 61.65 x 257 x 1
n2SO3 =
3.3+ 61.65+nS O 3
3
⟹n SO3 + 64.95 n2SO3 = 3.32 x 61.65 x 257
⇒ n2SO3 = 40.458
∴ 40.458 of SO3 came out unreacted from the 1st absorber and amount of SO3 i.e. absorbed.
= 96.7 – 40.458
= 56.242 x 80 k mol.
= 4499.36 kg.
SO3 absorbed by 98% H2SO4 (H2O + SO3 ⟶ H2SO4)

Let ‘W’ be the weight of 98% H2SO4 used in the absorption tower.
W x 0.02
SO3 absorbed by acid = ( ) x 80 kg.
18
=0.0889 W kg.
Total weight of 100% acid formed = W + 0.0889 W = 1.0889 W kg.
Kg. of SO3 absorbed by W kg = 1.0889 W – W

= 0.0889 W
But, we know
0.0889 W = 4499.36
31
⇒ W = 50611.47357 kg.
∴ Weight of 100% acid = 1.0889 w =55110.83357.

SO3 96 .7 7736 SO3 40.458 3236.64
SO2 3.3 211.2 SO2 3.3 211.2
O2 61.65 1972.8 O2 61.65 1972.8
N2 790 22120 N2 790 22120
98% H2SO4 (506.1147357+ 100% H2SO4 562.355

56.2497063) 50611.47357 55110.83357
=562.3497063
Total 1513.999706 82651.47357 Total 1457.76 82651.4735
Table: 6.4 Material Balance for 1st absorber
6.5 Second Contact:
Fourth Stage Reactor:-
In the 4th stage (2nd contact) 99.8% conversion of SO2 to SO3 is completed.
32
Inlet
(SO3 = 40.458 K mol
(SO3 = 43.558 K mol Outlet SO2 = 3.3 K mol
SO2 = 0.2 K mol O2 = 61.65 K mol
O2 = 60.1 K mol N2 =790 K mol)
N2 = 790 K mol)
Fig: 6.5 4th stage reactor
SO2 left = 3.3 – 100 x 0.031 = 0.2
3.1
SO3 formed = x 100 = 3.1
100
SO3 in the outlet = 40.458 + 3.1 = 43.558 K mol.
O2 used = 61.65 – (0.5 x 3.1) = 60.1 K mol.

SO3 40.458 3236.64 SO3 43.558 3484.64
SO2 3.52 211.2 SO2 0.2 12.8
O2 61.65 1972.8 O2 60.1 1923.2
N2 790 22120 N2 790 22120
Total 895.628 27540.64 Total 893.858 27540.64
33
Table: 6.5 Material Balance for 4th stage in the reactor.
6.6 Final Absorber: - (the gases after 2nd contact enters the final absorber where complete
absorption of SO3 takes place)
Exit Gases
98 % recycle H2SO4
(SO3 = 3484.64 kg
SO2 = 12.8 kg
O2 = 1923.2 kg
N2 = 22120 kg ) 100% H2SO4
Fig: 6.6 Final Absorber
Amount of SO3 to be absorbed = 3484.64 kg
Let, ‘W’ be the kg of 98% H2SO4 used.
0.02 x W
SO3 absorbed = (
18
) x 80 = 0.0889 W
Amount of 100% H2SO4 formed = W + 0.0889W
= 1.0889 W
34
Since, 0.0889 W = 3484.64
⇒ W = 39197.30034 kg.
∴ Amount of 100% H2SO4 = 1.0889 x 39197.30034 = 42681.94034 kg

SO3 43.558 3484.64 SO3 0 0
SO2 0.2 12.8 SO2 0.2 12.8
O2 60.38125 1923.2 O2 60.38125 1923.2
N2 790 22120 N2 790 22120
98% H2SO4 (391.9730034+ 100% H2SO4 435.5300035 42681.94034
43.55255593) 39197.30034
= 435.5255595
Total 1329.664809 66737.94034 Total 1286.111253 66737.94034
Table: 6.6 Material balance for Final Absorber.
6.7 Final Circulation Tank: - from the final absorber acid moves on to the circulating tank.
100 % H2SO4 98% H2SO4

A2 R2
TT
35
98% H2SO4 P W2 make up water

(Dilution water)
Fig: 6.7 Final Circulation Tank

Overall material balance: -
A2 + W 2 = P + R2
⇒ W 2 – P = A 2 – R2
⇒ W2 – P = 42681.94034 – 39197.30034
⇒ W2 – P = 3484. 64 kg
Amount of H2SO4 required for dilution of 100 % H2SO4 (42681.94034 kg) to H2SO4.
2
= 42681.94034 x
98
= 871.0600069 kg.
∴ W2 = 871.0600069 kg
A2 + W 2 = P + R2
⇒ 42681.94034 + 871.0600069 = P + 39197.30034
⇒ P = 4355.700007

100% acid 435.5300035 42681.94034 98% H2SO4 435.5255593 39197.30034
recycle
Water 48.39222261 871.0600069 98% H2SO4 48.39666174 4355.700007
to tank
Total 483.9222576 43553.00035 Total 483.922226 43553.00035
Table: 6.7 Material Balance for Final Circulation tank

36
6.8 Interpass Tank: - (Acid from the inter pass absorber enters the inter pass circulating tank.)
100% H2SO4 from 1st 98% recycle to 1st absorber

Absorber A1 = 55110.83357kg R1 =50611.47357kg
To product stream
P W1 make up water
(Dilution H2O)
to drying tower
R = 53165.7kg
97% H2SO4 from drying 98% H2SO4 from

Tower, S =53713.8 kg tank 2, T = 4355.700007kg
Fig: 6.8 Interpass Tank

Overall material balance: -
W1 + T + A1 +S = P + R + R1
⇒ W1 + 4355.700007 + 55110.83357 + 53713.8 = P + 53165.7 + 50611.47357
⇒ P – W1 = 9403.160007
Water balance: -
W1 +4355.700007 x 0.02+53713.8x0.03 =P x 0.02 + 53165.7 x 0.02 + 0.02 x 50611.47357
⇒ W1 + 1698.528 = P x 0.02 + 2075.543471
⇒ W1 – P x 0.02 = 377.015471
Solving, P = 9979.770896 kg, W1 = 576.6108889 kg

Component K mol Kg Component K mol kg
100% H2SO4 562.3554446 55110.83357 98% H2SO4 562.3497063 50611.47357
(tank 1) to recycle
37
Make-up H2O 32.033933827 576.6108889 98% H2SO4 590.73 53165.7

to drying
tower
97% H2SO4 621.18 53713.8 98% H2SO4 110.8863433 9979.770896
from drying to product
tower
98% H2SO4 48.39666674 5355.700007
from tank 2
Total 1263.96605 113756.9445 Total 1263.96605 113756.9445
Table: 6.8 Material Balance for Interpass Tank.
6.9 Overall Plant Material Balance: -
Sulphur 98% H2SO4
O2 N2
H2SO4 plant
N2 O2
H2O SO2
Fig: 6.9 Overall plant Material Balance

38

Sulphur 100 3200 98% H2SO4 110.8863433 9979.770896
O2 210 6720 N2 790 22120
N2 790 22120 O2 60.38125 1923.2
H2O 110.8761609 1995.770895 SO2 0.2 12.8
8
Total 1210.876161 34035.7709 Total 961.4675933 34035.7709
Table: 6.9 Overall Plant Material Balance
Chapter 7
Modified Material Balance
To design a 1000 TPD capacity H2SO4 acid plant:

Basis: 1 hour
For a period of 330 days in a year we have to produce 330000 tons of acid per year.
330000 x 103
330000 TPY of 98% acid = = 41666.67 kg/ hr of 98% H2SO4
24 x 330
From our initial material balance taking 100 K mol per hour or 3200 kg/ hr of elemental sulphur
as the basis, the quantity of 98% H2SO4 acid form = 9979.770896 kg/ hr.
39
41666.67
Therefore the scale up ratio for our required plant, R = = 4.175
9979.77
So, we now scale up our plant according to the ratio R = 4.175, by multiplying each input output
with this ratio.
Quantity of sulphur ‘S’ as feed = 3200 x 4.175 = 13360 kg = 417.5 K mol.
Assuming 100% conversion of S to SO2
S + O2 SO2
1
SO2 + O2 SO3
2
Total SO2 produced = 100 x 4.175 x 64 = 26720 kg = 417.5 K mol.
Total O2 required = 1.5 x 100 x 4.175 x 32 kg = 20040 kg = 626.25 K mol.
Some oxygen must be taken in excess. Assuming 40% excess O2 .
Total O2 required = 156 x 1.4 x 4.175 x 32 = 28056 kg. = 876.75 Kmol.
876.75 x 100 x 29
Dry air entering = = 121075 kg = 4175 K mol.
21
Assuming at 30% and 70% R.H. from psychometric chart = 0.0189 kg water / kg dry air.
Water entering with air = 0.0189 x 29000 x 4.175 = 2288.3175 kg = 127.12875 k mol.
Total wet air entering = 4175 + 127.12875 = 4302.12875 K mol.
7.1 Drying Tower: -
Q dry air (121075 kg)
P wet air ‘R’ 98% H2SO4

(123363.3175kg) (221966.7975 kg)
40
‘S’ 97% H2SO4

(224255.115 kg)
Fig: 7.1 Drying Tower

Amount of Material In:
Wet air (P) = 29548.1 x 4.175 = 123363.3175 kg.

98% H2SO4 entering (R) = 53165.7 x 4.175 = 221966.7975 kg
Amount of Material Out:
Dry air (Q) = 29000 x 4.175 =121075 kg.

97% H2SO4 leaving out (S) = 53713.8 x 4.175 = 224255.115 kg.

Wet air (P) 4302.12875 123363.3175 Dry air (Q) 4175 121075
98% H2SO4 2244.331083 221966.7975 97% H2SO4 2593.4265 224255.115
(R) (S)
Total 6546.459833 345330.115 Total 6768.4265 345330.115
Table: 7.1 Modified Material Balance for Drying Tower
7.2 Sulphur Burner: -

Sulphur (13360 kg)
41
Dry air SO2

(28056 kg) (26720 kg)
Fig: 7.2 Sulphur Burner.
Amount of material in:

Sulphur = 3200 x 4.175 =13360 kg.
Oxygen required = 6720 x 4.175 = 28056 kg
Nitrogen = 22120 x 4.175 = 92351 kg.
Amount of material out:

SO2 formed = 6400 x 4.175 = 26720 kg.
O2 remained = 3520 x 4.175 = 14696 kg.
N2 remained = 22120 x 4.175 = 92351 kg

S 417.5 13360 SO2 417.5 26720
O2 876.5 28056 O2 459.25 14696
N2 3298.25 92351 N2 3298.25 92351
Total 4592.5 133767 Total 4175 133767
Table: 7.2 Modified Material Balance for Sulphur Burner.

7.3 Reactor: -
Outlet1
Inlet 2
42
Outlet 2
Inlet 3
Outlet 3
Inlet 4
Outlet 4
Fig: 7.3 Monsanto Four Stage Reactor
In The 1st Bed of Catalyst: - 74% Conversion Is Attained:

SO2 entering = 6400 x 4.175 = 26720 kg
O2 required = 3520 x 4.175 = 14696 kg
N2 entering = 22120 x 4.175 = 92351 kg.
SO3 formed = 5920 x 4.175 = 24716 kg.
SO2 remained = 1664 x 4.175 = 6947.2 kg
O2 remained = 2336 x 4.175 = 9752.8 kg.
N2 leaving = 22120 x 4.715 = 92351 kg.

SO2 417.5 26720 SO3 308.95 24716
O2 459.25 14696 SO2 108.55 6947.2
N2 3298.25 92351 O2 304.775 9752.8
N2 3298.25 92351
Total 4175 133767 Total 4020.525 133767
43
Table: 7.3.1 Modified Material Balance for 1st bed of the Reactor
In The Second Bed of Catalyst: - 18.4 % Conversion Is Attained:
SO3 entering = 5920 x 4.175 = 24716 kg
SO2 entering = 1664 x 4.175 = 6947.2 kg
O2 entering = 2336 x 4.175 = 9752.8 kg
N2 entering = 22120 x 4.175 = 92351 kg.
SO3 leaving = 7392 x 4.175 = 30861.6 kg
SO2 remained = 486.4 x 4.175 = 2030.72 kg
O2 remained = 2041.6 x 4.175 = 8523. 68 kg.
N2 leaving = 22120 x 4.175 = 92351kg.

SO3 308.95 24716 SO3 385.77 30861.6
SO2 108.55 6947.2 SO2 31.73 2030.72
O2 304.775 9752.8 O2 266.365 8523.68
N2 3298.25 92351 N2 3298.25 92351
Total 4020.525 133767 Total 3982.115 133767
Table: 7.3.2 Modified Material Balance for 2nd bed of the Reactor
In The 3rd Bed of Catalyst: - 4.3% Conversion Is Attained:

44
SO3 entering = 486.4 x 4.175 = 30861.6 kg
SO2 entering = 7392 x 4.175 = 2030.72 kg
O2 entering = 2041.6 x 4.175 = 8523.68 kg
N2 entering = 22120 x 4.175 = 92351 kg.
SO3 formed = 7736 x 4.175 = 32297.8 kg
SO2 leaving = 211.2 x 4.175 = 881.76 kg
O2 leaving = 1972.8 x 4.175 = 8236.44 kg.
N2 leaving = 22120 x 4.175 = 92351kg.

SO3 385.77 30861.6 SO3 403.7225 32297.8
SO2 31.73 2030.72 SO2 13.7775 881.76
O2 266.365 8523.68 O2 257.38875 8236.44
N2 3298.25 92351 N2 3298.25 92351
Total 3982.115 133767 Total 3973.13875 133767
Table: 7.3.3 Modified Material Balance for 3rd bed of the Reactor
7.4 First Absorber: - SO3 = 13512.972 kg, SO2 = 881.76 kg
O2 = 8236.44 kg, N2 =92351 kg
98% H2SO4
(211302.9022)
Absorption
SO3 = 32297.8 kg
Tower
45
SO2 = 881.76 kg
O2 = 8236.44 kg
N2 = 92351 kg.
100% H2SO4
(230087.7302 kg)
Fig: 7.4 First Absorber

SO3 entering = 7736 x 4.175 = 32297.8 kg
SO2 entering = 211.1 x 4.175 = 881.76 kg
O2 entering = 1972.8 x 4.175 = 8236.44 kg
N2 entering = 22120 x 4.175 = 92351 kg

98% H2SO4 entering =50611.47357 x 4.175 = 211302.9022 kg
SO3 leaving = 3236.64 x 4.175 = 13512.972 kg
SO2 leaving = 211.2 x 4.175 = 881.76 kg
O2 leaving = 1972.8 x 4.175 = 8236.44 kg.
N2 leaving = 22120 x 4.175 = 92351kg.
100% H2SO4 leaving = 22110.83357 x 4.175 = 230087.7302 kg

46
SO3 403.7225 32297.8 SO3 13512.972

SO2 13.7775 881.76 SO2 168.91215 881.76
O2 257.38875 8236.44 O2 13.7775 8236.44
N2 3298.25 92351 N2 92351
98% H2SO4 2347.810024 211302.9022 100% H2SO4 257.38875 230087.7302
3298.25
2347.833982
Total 6320.948774 345069.9022 Total 6086.162382 345069.9022
Table: 7.4 Modified Material Balance for 1st Absorber.
7.5 Fourth Stage Reactor:
In the 4th stage (2nd contact) 99.8% conversion of SO2 to SO3 is completed.
Inlet
Outlet (SO3 = 13512.972 kg
(SO3 = 14548.372 kg SO2 = 881.76 kg
SO2 = 53.44 kg O2 = 8236.44 kg
O2 = 8029.36kg N2 = 92351 kg)
N2 = 92351 kg)
47
Fig: 7.5 Fourth Stage Reactor
SO3 entering = 3236.64 x 4.175 = 13512.972 kg
SO2 entering = 211.2 x 4.175 = 881.76 kg
O2 entering = 1972.8 x 4.175 = 8236.44 kg
N2 entering = 22120 x 4.175 = 92351 kg

SO3 formed = 3484.64 x 4.175 = 14548.372 kg
SO2 leaving = 12.8 x 4.175 = 53.44 kg
O2 leaving = 1923.2 x 4.175 = 8029.36 kg.
N2 leaving = 22120 x 4.175 = 92351kg.

SO3 168.91215 13512.972 SO3 181.85465 14548.327
SO2 13.7775 881.76 SO2 0.835 53.44 kg
O2 257.38875 8236.44 O2 250.9175 8029.36
N2 3298.25 92351 N2 3298.25 92351
Total 3738.3284 114982.172 Total 114982.172
3731.85715
Table: 7.5 Modified Material Balance for 4th bed of the Reactor
7.6 Final Absorber: - Exit gases

48
98% H2SO4
(163648.7289 kg)
(SO3 = 14548.372 kg
SO2 = 53.44 kg
O2 = 8029.36kg
N2 = 92351 kg) 100% H2SO4

(178197.1009 kg)
Fig: 7.6 Final Absorber

SO3 entering = 3484.64 x 4.175 = 14548.372 kg
SO2 entering = 12.8 x 4.175 = 53.44 kg
O2 entering = 1923.2 x 4.175 = 8029.36 kg
N2 entering = 22120 x 4.175 = 92351 kg

98% H2SO4 entering =39197.30034 x 4.175 = 163648.7289 kg.
SO3 leaving = 0 x 4.175 = 0
SO2 leaving = 12.8 x 4.175 = 53.44 kg
O2 leaving = 1923.2 x 4.175 = 8029.36 kg.
N2 leaving = 22120 x 4.175 = 92351kg.
100% H2SO4 leaving = 42681.94034 x 4.175 = 178197.1009 kg

49

SO3 181.85465 14548.372 SO3 0 0
SO2 0.835 53.44 SO2 0.835 53.44
O2 250.9175 8029.36 O2 250.9175 8029.36
N2 3298.25 92351 N2 3298.25 92351
98% H2SO4 1818.31921 163648.7289 100% H2SO4 1818.337764 178197.1009
Total 5550.17636 278630.9009 Total 5368.340264 278630.9009
Table: 7.6 Modified Material Balance for Final Absorber
7.7 Final Circulation Tank:
100 % H2SO4 98% H2SO4

A2 R2
TT
98% H2SO4 P W2 (make up water)
Figure No. 7.7 Final Circulation Tank

100 % acid (H2SO4) = 42681.94034 x 4.175 = 178197.1009 kg
Water = 871.0600069 x 4.175 = 3636.675529 kg

98% H2SO4 recycle = 391.97.30034 x 4.175 = 163648.7289 kg
50
98% H2SO4 to tank = 18185.04753 kg

100 % acid 1818.337764 178197.1009 98% H2SO4 1818.31921 163648.7289
(H2SO4) recycle
Water 202.0375294 3636.675529 98% H2SO4 to 202.0560837 18185.04753
tank
Total 2020.375293 181833.7764 Total 2020.375293 181833.7764
Table: 7.7Modified Material Balance for Final Circulation Tank
7.8 Interpass Tank:
Absorber A1 R1
To product stream
P W1 make up water
(Dilution H2O)
To drying tower
R
H2SO4 from drying T

Tower, S
Fig: 7.8 Interpass Tank

100% H2SO4 (tank 1) = 55110.83357 x 4.175 = 230087.7302 kg.
Make up H2O = 576.6108889 x 4.175 = 2407.350461 kg.
97% H2SO4 from drying tower = 53713.8 x 4.175 = 224255.115 kg.
98% H2SO4 (tank 2) = 4355.700007 x 4.175 = 18185.04735 kg.

98% H2SO4 to recycle = 50611.47357 x 4.175 = 211302.9022 kg
51
98% H2SO4 to drying tower = 53165.7 x 4.175 = 221966.7975 kg.

98% H2SO4 to product stream = 9979.770896 x 4.175 = 41665.54349 kg

100% H2SO4 2347.833982 178197.1009 98% H2SO4 to 2136.698913 211302.9022
Make-up H2O 133.7416923 2407.350461 recycle
98% H2SO4 2257.043167 224255.115 98% H2SO4 to 2466.29775 221966.7975
from D.T. D. T.
98% H2SO4 202.0260837 18185.04753 98% H2SO4 to 421.2838166 41665.54349
(tank 2) P.S.
Total 4940.674925 474935.2432 Total 5024.28048 474935.2432
Table: 7.8 Modified Material Balance for Interpass Tank

In the above table D. T. = drying tower, P.S. = product stream
7.9 Overall Plant Material Balance: -
Sulphur 98% H2SO4

52
O2 N2
N2 O2
H2O SO2
Fig: 7.9 Overall Plant Material Balance.

Sulphur entering= 3200 x 4.175 =13360 kg.
O2 entering = 6720 x 4.175 = 28056 kg
N2 entering = 22120 x 4.175 = 92351 kg.
H2O entering = 1995.770896 x 4.175 = 8332.34349 kg

98% H2SO4 formed = 9979.770896 x 4.175 = 41665.54349 kg
SO2 leaving = 12.8 x 4.175 = 53.44 kg.
O2 leaving = 1923.2 x 4.175 = 8029.36 kg.
N2 leaving = 22120 x 4.175 = 92351 kg

Sulphu 417.5 13360 98% H2SO4 462.9504832 41665.54349
formed
O2 876.75 28056 O2 250.9175 8029.36
N2 3298.25 92351 N2 3298.25 92351
H2O 462.9079717 8332.34349 SO2 0.835 53.44
Total 5055.407972 142099.3435 Total 4012.952983 142099.3435
Table: 7.9 Overall Plant Modified Material Balance

53
Chapter 8
Energy Balance
Basis: 1 hour operation
In carrying out the energy balance, these following assumptions have been made:
a) There is no energy loss from the equipments by radiation.

b) There is no accumulation of heat.
c) All the process equipments are under atmospheric pressure.
d) Datum temperature is 25oC.
e) Water for cooling is available at 20oC.
Chemical Data: (Ambient temperature 25oC)
Specific heats: (KJ/Kmol°K) (valid in range 250K to 500K)
Heat capacities of gases at constant pressure
Cp = a + bT + cT2 + ….
N2 = 27.034 + (5.815×10-3) T – (0.2889×10-6) T2 ------------------------6.1-1
O2 = 25.611 + (13.260×10-3) T – (4.2077×10-6) T2 -----------------------6.1.2
SO2 = 29.077 + (41.910×10-3) T – (15.8847×10-6) T2 --------------------6.1.3
SO3 = 31.208 + (80.093×10-3) T – (27.7501×10-6) T2 ---------------------6.1.4

(Ref. Narayanan K.V, Lakshmikutty B, Stoichiometry and Process Calculations )
54
S = 3.63 + (0.00640T)(Kcal/kmol°K) ---------------------------------------6.1.5
100% H2SO4 =1.4435 KJ/kg K
98% H2SO4 = 1.465 KJ/ kg K
97% H2SO4 = 1.4865 KJ/ kg K
H2O = 4.187 KJ / kg K
Heat of Combustion of Sulphur = - 296.77 KJ/kmol
Heat of reaction for [SO2 + ½ O2 SO3] = ∆ Hr = 96.270 KJ/gmol
Heat of dilution = 9.304 KJ/kg of H2O
Heat of vaporization of water at 25oC = 2430.96 KJ/kg (Ref. Perry R.H, Green D.W ,Chemical
Engineer’s Hand book)
8.1: Drying Tower:
Q (Dry air) (O2 + N2)
Mesh pad
R (98%H2SO4)
P (wet Air)
55
S (97% H2SO4)
Figure 6.1: Drying Tower
The input streams are at a temperature of 30oC (303K)
Cp O2 = 29.242 KJ/ kmol K Cp N2 = 28.769 KJ/ kmol K
Cp H2O = 4.187 KJ/ Kg K Cp 98% H2SO4 = 1.465 KJ/ Kg K
Cp 97% H2SO4= 1.4865 KJ/ Kg K Heat of dilution= 9.304 KJ/Kg
Now, Heat input
= mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mH2O Cp H2O ∆T + mH2SO4 Cp H2SO4 ∆T

= 876.75×29.242× (30-25) + 3298.25×28.769× (30-25) + 2288.3175×4.187× (30-25) +
(221966.7975×1.415× (30-25))
=2276439.107 KJ
Heat Generation (due to dilution) = 2288.3175×9.304 = 21290.50602 KJ
Heat Output (neglecting changes in Cp values at output temperature To
= mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mH2SO4 Cp H2SO4 ∆T
= (876.75×29.242 × (To-25)) + (3298.25×28.769 × (To-25)) + (224255.115×1.4865 × (To-25))
= 453880.5062 × (To-25)
Assuming steady state and no heat loss:
The heat balance equation is given as

56
Input + Generation = Output
2276439.107 + 21290.50602 = 453880.5062 × (To-25)
Solving,
2297729.613
T o= + 25 = 30.0624oC
453880.5062
TABLE N0 8.1
ENERGY IN ENERGY OUT
( Input + Generation )
Component Enthalpy Component Enthalpy

KJ KJ
O2 128189.6175 O2 129789.4239
N2 474436.7713 N2 480357.7422
H2O 47905.9269 97% H2SO4 1687577.511
Heat of 21290.50602
Dilution
98% H2SO4
1625906.792
Total 297729.613 Total 2297724.677

57
8.2: AIR PREHEATER
Hot gases at a temperature of 1000oC come from the Sulphur furnace. Air from the dryer is
heated to 60oC before it enters the burmner in a Preheater.
Air from dryer at 30.0624oC to WHB 1
Air to burner at 100oC hot gases from burner at 1000oC
Figure 6.2: Air preheater

58
Cp of components of air at 60oC (333K)
N2 = 28.16 KJ/ kmol K O2 = 29.97 KJ/ kmol K
Enthalpy input of the air = 610147.1661 KJ
Output Enthalpy = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T
= 876.75×29.97× (60-25) + 3298.25×29.16× (60-25) = 4285860.863KJ
Cp of Hot gas components of air at 1000oC (1273K)
N2 = 32.97 KJ/ kmol K O2 = 35.67 KJ/ kmol K SO2 =56.69 KJ/ kmol K
Input Enthalpy of the hot gases mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + m SO2 Cp SO2∆T

=459.25 ×35.67×(1000-25) + 3298.25×33.97×(1000-25) + 417.5×56.69 ×(1000-25) =
148288798.16KJ
Assuming no heat loss,
Heat gained by the cold air stream = 4285860.863 – 610147.1661 = 3675713.697KJ
(Heat lost by hot gas steam)
Output Enthalpy of the Hot gas stream =1482887968.16 – 3675713.697 = 144612388.9 KJ
The heat lost is negligible compared to the heat input and Input, output Enthalpy are comparable.
Therefore, we neglect the change in Cp due to drop in temperature,
Heat output =417.5 ×56.69×(T0-25) + 459.23×35.67×(T0-25) + 3298.25×33.97 ×(T0-25)
= 152090.3616(T0-25)
Making heat balance,
144612388.9 = 152090.3616 (T0-25)

59
144612388.9
T o= + 25 = 975.832oC
152090.3616
Energy In Energy Out

Component Enthalpy KJ Component Enthalpy KJ
Air Input 610147.1661 Air output 4285860.863
Hot gas input 148288102.6 Hot gas output 144612388.9
Total 148898249.8 Total 148898249.8
Table 8.2
8.3: Sulphur-Melter
Solid Sulphur at 30oC Molten Sulphur at
Heat from fuel
Figure 6.3: Sulphur Heater
Cp of sulphur at 30oC = 23.32 KJ/ Kmol K
Cp of sulphur at 140oC = 26.26 KJ/ Kmol K

60
Enthalpy input of Sulphur = mS CpS ∆T = 417.5 ×23.32 × (30-25) = 48680.5 KJ
Enthalpy output of Sulphur = mS CpS ∆T = 417.5 ×26.26 × (140-25) = 1260808.25KJ
Therefore, heat supplied by heater = 1260808.25- 48680.5 = 1212127.75KJ
TABLE No. 8.3
Component Enthalpy Component Enthalpy KJ

KJ
Sulphur 48680.5 Sulphur 1260808.25
Heat supplied 1212127.75
Total 1260808.25 Total 1260808.25

61
8.4: Sulphur Burner
Sulphur at 140oC
SO2 O2 N2 at 1000oC
O2 N2 at 100oC
Heat from oil fired burner
Fig 8.4: Sulphur Burner
S + O2 SO2 ∆ H= -70.9 Kcal/Kmol = -296.77 KJ/ kmol ----------------6.4.1

Standard heat of combustion = 296.77 KJ/ kmol
The heat of reaction at any temperature is given by (Narayanan and Lakshmikutty,
2005).
∆ HT0 = ∆H’ + ∆ α T + ∆ (β/2) T2 + ∆(δ/3) T3 -------------------- 6.4.2
Where ∆ α,∆ β , ∆δ are difference in coefficients of the Cp equation of the product and
the reactants
∆H’ is evaluated from the heat of a single reaction
The specific heat of the components are represented by Cp = α + βT + δT2 ----- 6.4.3
TABLE No. 8.4.1

62
Component Α Β δ
SO2 29.077 41.910 × 10-3 -15.8847 × 10-6
O2 25.611 13.260 × 10-3 -4.2077 × 10-6
S 15.19 0.02619 0
∆ α = α SO2 - α S- α O2
= 29.077 –25.611–15.19 = –11.724
∆ β = β SO2– β s- β O2
= 41.910× 10-3 - 0.02679-13.260× 10-3 = 1.86× 10-3
∆ δ = δ SO2 - δ S - δ O2
= (-15.8847) × 10-6 – 0 – (-4.2077 × 10-6) = -11.677 × 10-6
∆ HT0 = ∆H’ -11.724T + ∆ (1.86× 10-3/2) T2 + ∆(-11.677 × 10-6/3) T3
At 298K, ∆ H2980 = -296.77 KJ/Kmol K

So, putting this in above equation and solving for ∆H’
∆H’ = -296770 –11.724 ×298 + ∆ (1.86 × 10-3/2) (298)2 – ∆(-11.677 × 10-6/3) (298)3
∆H’ = – 300284.1694
Now, ∆ HT0 = -300284.1694 -11.724 T + ∆ (1.86 × 10-3/2) T2 + ∆(-11.677 × 10-6/3) T3
At T = 100OC = 1273K,
∆ H9730 = -300284.1694 -11.724 (1273) + ∆ (1.86 × 10-3/2) (1273)2 + ∆(-11.677 × 10-6/3) (1273)3
∆ H973 = -321.731KJ/ kmol
Temperature inside the burner 1000oC, (Anderson and Wenzel, 1961)

We assume the output gas from burner to be 1000oC
Input enthalpy of air (N2 + O2) = 4285860.863 KJ
Enthalpy input of Sulphur = m Cp ∆T = 417.5 ×26.26 × (140-25) = 1260808.25KJ
63
Heat generated due to combustion = 321.731 × 417.5 = 134322.6925 KJ
Heat output from burner = 417.5 ×56.69× (1000-25) + 459.25×35.67× (1000-25) +

3298.25×32.97 ×(1000-25)
= 148288798.1 KJ
Heat given/ generated by the burner = 148288798.1 – 4285860.863 – 1260808.25 – 134322.6925

= 142607806.3 KJ
TABLE No. 8.4.2

KJ
O2 919666.9125 O2 15971911.31
N2 3366193.95 N2 109240513.7
S 1260808.25 SO2 23076373.13
Generation 134322.925
Burner 142607806.3
Total 148288798.1 Total 148288798.1

64
8.5: Waste Heat Boiler 1 (WHB1)
SO2 SO2
O2 N2
N2 O2 (at 410oC)
(At 6750C)
Fig 8.5: Waste Heat Boiler
From literature (Shreve, Dryden), we know the entry point temperature to the four stages
of reactor,
1st Stage=4100C
2nd Stage=4380C
3rd Stage = 4320C
4th Stage = 4270C
WHB1 is just before the first stage entry point. So it must absorb heat to reduce the
temperature of gases from 6750C to 4100C
Therefore, Cp of the component at

TABLE No. 8.5.1
Component At Input (975.8320C) At Output (4100C)
(KJ/Kmol K) (KJ/Kmol K)
O2 35.669 32.70
N2 33.969 30.87
SO2 56.689 50.291
65
Heat input = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T

= (459.25×35.669× (975.832-25)) +(3298.25×33.969×(975.832-25)) +
(417.5×56.689×(975.832-25))
=144613084.5KJ
Heat output = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T

= (459.25×32.7×(410-25)) + (3298.25×30.87×(410-25)) +(417.5×50.291×(410-
25))
= 53064913.83 KJ
Steam is generated at 4 Kgf/cm2 and 300oC.
Heat absorbed in generating steam = 144609661.8 – 53064913.83 = 91544747.97 KJ

Saturation temperature at 4Kgf / cm2(3.92 bar) = 142.89oC
Latent heat, λs = 2135.14 KJ/Kg
Cp of steam at 300oC = 1.9703 KJ/KgoK
Cp of water = 4.187KJ/KgoK
Let, amount of water = m = amount of steam.
Q = m Cp w ΔT1 + m λs + m Cp s ΔT2
 91125465.25 = m (2917.364)
91125465.25
 Steam generated = = 31235. 546 kg
2917.364
TABLE NO. 6.5.2

KJ KJ
O2 15575567.82 O2 5781727.875
N2 22503966.12 N2 39199536.34
66
SO2 106529557.4 SO2 8083649.613
Heat -91548170.63
absorbed
Total 53064913.83 Total 53064913.83
8.6: Reactor
Reaction
SO2 +1/2O2 SO3 ∆ Hr = ΔHof – ΔHoreactant
= -395.18 – (-296.90)
= -98280 J/gmol
= 96270 KJ/kmol-------6.6.1
The heat of reaction at any temperature is given by ( Narayanan and Lakshmikutty, 2005)
∆ HT0 = ∆H’ + ∆ α T + ∆ (β/2) T2 + ∆(δ/3) T3 ----------------------6.6.2
TABLE NO. 6.6.1

Component α Β δ
SO2 29.077 41.910 × 10-3 -15.8847 × 10-6
O2 25.611 13.260 × 10-3 -4.2077 × 10-6
SO3 31.208 80.093 × 10-3 -27.7501 × 10-6
∆ α = α SO3 - 1/2 α O2 - α SO2

= 31.208 – ½ (25.611) -29.077 = -10.6745
67
∆ β = β SO3 - 1/2β O2 - βSO2

= (80.093-1/2(13.260)-41.910) × 10-3 = 31.553 × 10-3
∆ δ = δ SO3 - 1/2 δ O2 - δ SO2

= [(-27.7501)-1/2(-4.2077)-(-15.8847)] × 10-6 = -9.76155 × 10-6
∆ HT0 = ∆H’ -10.6745 T + ∆ (31.553 × 10-3/2) T2 + ∆(-9.76155× 10-6/3) T3 -----6.6.3
At 298K, ∆ H2980 = -98. 280 KJ/gmol
At T= 683K,
∆ HT0 = -9641.907 -10.6745(683) + ∆ (31.553 × 10-3/2) (683)2 + ∆(-9.76155× 10-6/3) (683)3
∆ H683 = -97381.74 J/gmol
Similarly,
∆ H7110 =-97197.64 KJ/ kmol
∆ H7050 =-97238.27 KJ/ kmol
∆ H7000 = -97271.64 KJ/ kmol
Reactor
6.6.a: Stage 1
SO2 N2 O2
at 4100C
68
SO2
O2
SO3
N2 at 6010C
Figure 6.6.a: Reactor stage1
Therefore, Heat input (at Cp values of T = 410OC)

= mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T
= (417.5×50.291× (410-25)) + (459.25×32.7×(410-25)) + (3298.25×30.87×(410-25))
= 53064913.83 KJ
Heat of generation = 308.95×97381.74 = 30086088.57 KJ

Since the heat generated is not within considerable limits but we can’t neglect the change
in Cp values due to rise in temperature to T0 in comparison to heat input.. So we consider Cp
value at 600OC (873K).
Heat output = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T+ mso3 Cp so3 ∆T

=108.55×53.55×(T0 –25)+254.775×33.98×(T0 –25)+3298.25×31.89×(T0 –25)+258.95×79.98×(T0
– 25) = 146060.1205(T0 – 25)
69
Therefore, making a steady state heat balance with no loss,
53064913.83 + 30086088.57 = 146060.1205(T0 – 25)
883151002.4
T o= +25 = 594.29oC (which is comparable to assumed temperature)
146060.1205
TABLE NO. 6.6

KJ KJ
O2 8083649.613 O2 5895712.124
N2 39199536.34 N2 59878601.08
SO2 5781727.875 SO2 3309198.8
Heat of 30086088.57 SO3 14067054

Generation
Total 83151002.4 Total 83151004.18
6.7: Waste Heat Boiler 2 (Whb2)
The gas excluding from the first stage reactor at 590.4OC (863.4 K) is cooled to 438
O
C (711K) before it enters the 2nd Stage in the Waste heat Boiler 2 (WHB2)
70
SO2 SO2
O2 N2
N2 O2
SO3 at 594.2930C SO3 at 4380C
Figure 6.7: Waste Heat Balance

Cp values (KJ/Kmol K) at:
Table No 6.7.1
Component At Input (594.2930C) At Output (4380C)
(KJ/Kmol K) (KJ/Kmol K)
O2 33.98 32.90
N2 31.89 31.02
SO2 53.55 50.88
SO3 79.98 74.11
Heat input
= mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T+ mso3 Cp so3 ∆T
= (304.775×33.98× (594.293-25)) + (108.55×53.55× (594.273-25)) +
(3298.25×31.89×(594.293-25))
+ (308.95×79.98× (594.293-25))
= 83151004.18 KJ
= (304.775×32.91× (438-25)) + (108.55×50.84× (438-25)) + (3298.25×31.02×
(438-25)) + (308.95×74.11× (438-25))
= 58133103.97KJ
Saturated steam is generated at 1.023 Kg/cm2 water at 30oC is available.
Saturation temperature = 100oC
Cp = 4.187 KJ/Kg K
λs = 7256.9 KJ/Kg
71
Heat absorbed = 83151004.18 KJ – 58133103.97 KJ = 25017900.21 KJ

Let, m = amount of water = amount of steam.
 25017158.76 = m Cpw (100-30) + m λs
25004399.13
Steam produced = = 10057.15 Kg
2549.99
TABLE NO. 6.7

KJ
O2 59878916.62 O2 4142449.988
N2 5895743.193 N2 42254738.3
SO2 3309216.238 SO2 2279215.666
SO3 14067128.13 SO3 9457441.46
Heat
absorbed 25017158.76
Total 58133845.42 Total 58133845.42
6.6.b: Reactor
b) Stage 2 (Input temperature = 4380C,
Output temperature =T0)
SO2
O2
N2
SO3 at 4380C
SO2
O2
72
N2
SO3 at 70
Figure 6.6.b: Reactor Stage 2
Heat input (711K) = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mSO2 Cp SO2 ∆T+ mSO3 Cp SO3 ∆T
= (304.775×32.91× (438-25)) + (108.55×50.84×(4N38-25)) +
(3298.25×31.02×(438-25)) + (308.95×74.12×(438-25))
= 58133845.42KJ
Heat generated = 76.82×97197.64 = 7466722.705 KJ
Assumption, the heat generated is within considerable limits compared to the heat input.
We can neglect the changes in Cp values to rise in temperature to T0
Heat output (at Cp for 711K) = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T+
mso3 Cp so3 ∆T
(31.73×50.84× (T0-25)) + (266.365×32.91× (T0-25)) + (3298.25×31.02× (T0-25))
+ (385.77×74.12× (T0-25))
= 141284.2128(T0-25) KJ

58133845.42 + 7466722.7055= 141284.2128(T0 – 25)
65600568.13
T o= + 25 = 489.316 oC
141284.2128
TABLE NO. 6.6.b

73
KJ KJ
O2 4142449.988 O2 13276313.87
N2 2279215.666 N2 47504966.26
SO2 42254738.3 SO2 749012.8412
SO3 9457441.462 SO3 4070227.556
Total 65600568.12 Total 65600520.53
6.6. C: Stage 3(Input temperature = 4320C,

Output temperature =T0)
SO2
O2
N2l
SO3 l at 4320C
SO2,O2 , N2 , SO3
Fig No 6.6.c Reactor 3rd stage
Cp value at input temperature = 4320C Cp ( KJ/Kmol K)

74
SO2-50.73 O2- 32.86

N2-30.98 SO3- 73.70
Now, Heat Input = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp SO2 ∆T+ mSO3 Cp SO3 ∆T
(266.365×32.86× (432-25)) + (31.73×50.73×(432-25)) + (3298.25×30.98×(432-25))
+ (385.77×73.7×(432-25))
= 57376194.48 KJ
Heat generated = 17.9525× 97238.27 = 1745670.042 KJ
Heat output (neglecting change in Cp) = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T+ mso3
Cp so3 ∆T
(13.7775×50.73× (T0-25)) + (257.38875×32.86× (T0-25)) + (3298.25×30.98×
(T0-25)) + (403.7225×73.70× (T0-25))
= 141090.8602(T0-25) KJ
57376194.48 + 1745670.042 = 141090.8602(T0 – 25)
59121864.52
T o= +25 = 444.033oC
141090.8602
TABLE No. 6.6.c


KJ KJ
75
O2 3562370.837 O2 3544094.929
N2 41587172.5 N2 42816701.85
SO2 655732.8 SO2 292875.8137
SO3 11571518.34 SO3 12468053.81
Heat of 1745670.042
reaction
Total 59121864.52 Total 59121726.42
6.6.d: Stage 4 (inlet temperature = 4270C, output temp = T0)
SO2
O2
N2
SO3 at 4270C
SO2
O2
N2
SO3 at T0
Figure 6.6.d Reactor 4th stage
76
SO2-50.63 O2- 32.83

N2-25.96 SO3- 73.67
Heat Input = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp SO2 ∆T+ mso3 Cp SO3 ∆T
= (257.38875×32.83× (427-25)) + (13.7775×50.63× (427-25)) + (3298.25×30.96× (427-25))
+ (168.91215×73.67× (427-25))
= 49729492.64KJ
Heat generated = 12.9425×97271.64 = 1258938.201 KJ
Heat output (neglecting change in Cp) = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mSO2 Cp SO2 ∆T+ mso3
Cp SO3 ∆T
= (0.835×50.63× (T0-25)) + (250.9175×32.83× (T0-25)) + (3298.25×30.96× (T0-25))
+ (181.9425×73.67× (T0-25))
= 123790.9496(T0-25) KJ
49729492.64 + 1258938.201= 123790.9496 (T0 – 25)
50988430.84
T o= +25 = 436.891oC= 437oC
123790.9496
TABLE No. 6.6d

ENERGY IN ENERGY
OUT

KJ KJ
O2 3396929.21 O2 3393002.168
N2 41049755.64 N2 420059763.43
SO2 280417.0397 SO2 17413.12451

77
SO3 5004992.46 SO3 5512956.01
Total 50967247.08 Total 50988378.02
6.8: Hot Interpass Exchanger (Heat Exchanger 1)
Hot (488.317oC) T c in
2nd stage outlet
432oC
3rd stage inlet
4th stage inlet (427oC)

78
Figure 6.8 Hot Inter pass exchanger
Hot fluid:
Outlet gas from the stage 2 of the reactor at 488.317oC which is cooled to a temperature of
432oC and fed into stage 3 inlet
So, Q h in = 65459377.62 KJ Q h out = 57376194.48KJ
Th in = 488.317oC Th out = 432oC
Cold Fluid:
Gas from the cold inter pass exchanger at Tc in which gets heated to 427oC before entering the 4th
stage inlet
Tc out = 427oC Q c out =49732094.35KJ
Assuming no heat loss, Heat absorbed by the cold stream:
Q h in – Q h out = 65600520.55 KJ - 57376194.48KJ = 8224326.07KJ
Q c in = Qc out – 8224326.07KJ = 41505166.57 KJ
So, the heat absorbed by the cold stream is not very high compared to the input and output
streams. Change in Cp at Tc in is neglected.
Q c in = (257.38875×32.83× (Tc in-25)) + (13.7775×50.63× (T c in-25)) + (3298.25×30.96× ( T c in-

25)) + (168.91215×73.67× (T c in-25))
= 123705.2056 ( T c in – 25 ) = 41505166.57
41648911.21
T c∈¿ + 25 = 360.517oC
123711.6775
TABLE No. 6.8

79
Component Heat Component Heat KJ

KJ
Hot input 65600520.55 Hot output 57376194.48
Cold input 41505166.57 Cold output 49729492.64
Total 107105687.1 Total 107105687.1
6.9: Cold Interpass Exchanger (Heat Exchanger 2)
Cold in
Hot (443.8oC) (1st absorber top at 90oC)

3rd stage outlet
Hot out (to secondary

Economizer)
Cold out (362oC)
80
Figure 6.9: Cold Interpass Exchanger
Hot fluid:
Outlet gas from the 3rd stage of the reactor at 444.033oC which is cooled to a certain temperature
before entering a secondary economizer.
So, Q h in = 59121303.15 KJ Th in = 443.033oC
Cold Fluid:
Gas from the top of first absorber column at 90oC (assumed) heated to a temperature of 362oC
which then enters the hot inter pass absorber
Tc in = 90oC T c out = 360.517oC Q c out =41505199.47 KJ
We assumed the cold inlet to be at 90oC (363K)
SO2-42.19 O2- 29.86 N2-29.10 SO3- 56.62

Q c in = (257.38875×29.86× (90-25)) + (13.7775×42.19× (90-25)) + (3298.25×29.10× (90-25))
+ (168.91215×56.62× (90-25)) = 7397635.813 KJ
Now, by assuming no heat loss,
Heat gained by cold stream =41505199.47 KJ –7397635.813 KJ = 34107563.66 KJ
= Heat lost by hot stream
Qh out =59121303.15 –34107563.66 = 25013739.49 KJ
Again Q h out (at Cp value for 3rd stage inlet) =
(403.7225×73.70× (T h out-25)) + (13.7775×50.73× (T h out-25)) + (3298.25×30.96× (T h out-25))
+ (257.38875×32.86× (T h out-25)) = 141090.8602 × (T h out – 25)
141024.8952 (T h out – 25) = 25013739.49
25013739.49
T o= +25 = 202.371oC
141024.8952
TABLE 6.9
81
Component Heat Component Heat KJ

KJ
Hot input 59121303.15 Hot output 25013739.49
Cold input 7397635.813 Cold input 41505199.47
Total 66518938.96 Total 66518938.96
8.10: SECONDARY ECONOMIZER ( COOLER 1)
The hot gases for cold IP Exchanger is further cooled from 201oC to 110oC (assumed) at
which it enters the bottom of the first absorption tower.
Hot gases from cold IP exchanger at 202.371oC
At To = 110oC
Figure 6.10: - Secondary Economizer
Inlet gas temperature = 202.371oC (475.371K)

Outlet gas temperature = 110oC (383K)
Cp values (KJ/kmol K) at inlet and outlet:

82
TABLE NO. 6.10 a

Component At Input (2040C) (KJ/Kmol At Output (1100C)
K) (KJ/Kmol K)
O2 32.86 30.07
N2 30.96 29.21
SO2 50.73 42.79
SO3 73.70 57.81
Heat input = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T+ mso3 Cp so3 ∆T

(403.7225×73.70× (202.371-25)) + (13.7775×50.73×(202.371-25)) +
(3298.25×30.96×(202.371-25)) + (257.38875×32.86× (202.371-25))
= 25013726.68 KJ
(403.7225×57.81× (110-25)) + (13.77775×42.79×(110-25)) +
(3298.25×29.21×(110-25)) + (257.38775×30.07× (110-25))
= 10880875.43KJ
Heat absorbed =25013726.68KJ - 10880875.43KJ = 14132851.25KJ

Let, water temperature increase from 30oC to 80oC
m Cp w (To - 30) = 14132851.25
 m × 4.187 (80 - 30) = 14132851.25
14132851.25
Steam produced = = 5676.84kg
2430.96
TABLE NO.6.10

KJ KJ
83
O2 1500167.437 O2 657872.7756
N2 18112030.37 N2 8189060.013
SO2 123970.3698 SO2 50110.83413
SO3 5277558.503 SO3 1983831.807
Heat
absorbed 12378989.68
Total 10880875.43 Total 10880875.43
8.11: Intermediate Absorption Tower:

Q recycles at 30oC
SO3,O2,N2,SO3 at 900C
Qout – 7397959.127KJ
Q gen
SO2 O2 N2 SO3
Qin – 10880875.43KJ
110oC Q (100% H2SO4)
Fig 8.11: first absorption tower
SO3 + H2O H2SO4

Heat of formation of H2SO4 = - 130000KJ/ kmol
84
Therefore,
Q heat gen = 234.81 ×(-13000) = -30521530 KJ
Q recycle = 211302.9022 ×1.465× (30-25) = 1547793.759 KJ
Q in = 10880875.43
Q(100% H2SO4) = 230087.7302 ×1.4435× (T0-25)
=332131.6385(T0 -25) KJ
Making a steady state heat balance around the absorption tower
Q in + Q gen + Q recycle = Q out + Q 100% H2SO4
10880875.43 + 30521530 + 1547793.759 = 7397635.813+ 332131.6385(T0 -25)
 TO = 132.0436oC
TABLE NO.6.11
INPUT + GENERATION OUTPUT
Component Heat (KJ) Component Heat (KJ)
Q in 10880875.43 Q out 7397635.813
Q recycle 1547793.759
Q gen 30521530 Q (100% H2SO4) 35552566.26
Total 42950197.19 Total 42950202.08
8.12: Economizer
Outlet from the fourth stage of the reactor at 436.891 oC is fed into the economizer super heater
which cools it to 110oC, then it enters the bottom of the final absorbing tower.
SO2 , O2, N2, SO3 at 436.891o C

85
Steam at 100oC At 300oC
At 110oC
Figure 6.12:- Economiser
Q in = 50988378.02KJ (from 4th stage outlet)
Cp value at outlet temperature = 1100C Cp (KJ/Kmol K)
SO2-42.79 O2- 30.07

N2-28.21 SO 3- 57.81
Q out = mo2 Cp O2 ∆T + mN2 Cp N2 ∆T + mso2 Cp so2 ∆T+ mso3 Cp so3 ∆T

= 181.85465×57.81× (110-25) + 0.835×42.79×(110-25)+250.9175×30.07×(110-25)
+3298.25×29.21× (110-25) = 9727036.089 KJ
Heat absorbed =50967150.88KJ - 9727036.089KJ = 41261341.93 KJ

 m × 1.9702 × (300-100) = 41261341.93
41261341.93
Steam produced=m = =104713.587 kg
394.04
TABLE NO. 6.14
Component Enthalpy KJ Component Enthalpy KJ
O2 3391412.307 O2 641332.5841
N2 42040055.47 N2 3037.02025
SO2 17404.96523 SO2 8189060.013
SO3 5518278.119 SO3 8189060.013
Heat absorbed 41261341.93
Total 9727036.09 Total 9727036.09

86
8.15: Final Absorption Tower:
SO 2
O2 Qout at 90oC
N2
41750kg of 98% H 2SO4
Q rec
Q gen
at 110oC
SO2
O2
N2
SO3
Q 100% H2SO4
H 2S2O7 +97% H2SO4
Figure 6.15: FINAL ABSORPTION TOWER

87
Q in = 9727036.089 KJ
Q out = 0.835×42.79× (90-25) +250.9175×29.86×(90-25) +3298.25 ×28.99 × (90-25)

= 6727935.513 KJ
Q gen = 181.8319 × -130000 = 23638147 KJ

Q recycle = 163648.7289 × 1.465 × (30-25) = 1198726.939 KJ
Q 100% H2S04 178197.1009 ×1.4435 × (T0 -25) = 2572275.515 (T0 -25) KJ
Making a steady state heat balance around the absorption tower
Q in + Q gen + Q recycle = Q out + Q 100% H2S04
 9727036.089 + 23638147 + 1198726.939 = 6727935.513 + 2572275.515 (T0 -25)
2572275.515 (T0 -25) = 27835974.52
27835974.52
T o= +25 = 133.215 o C
79163.91365
TABLE NO.6.15
Q in 9727036.089 Q out 6727935.513
Q recycle 1198726.939
Q gen 23638147 Q 100% H2S04 27835978.44
34563910.03 34563913.96
88
6.16: FINAL CIRCULATING TANK
98% H2SO4 at T0
100%
H2SO4
Qin
Make up H2O at 133.215 oC
at 30oC (Qw)
Figure 6.16: FINAL ABSORBER CIRCULATING TANK
Q in = 3636.675529 ×4.187 × (30 -25) = 76133.8022 KJ

89
Q w = 178197.1009 × 1.4435 × (133.215 -25) = 27835978.44 KJ
Q gen = heat of dilution =9.304 × 3636.675= 33835.62912 KJ
Q out = 181833.7764 × 1.465× (T0-25) = 266386.4824(T0-25)
Making a steady state heat balance of the tank
Q in + Q w + Q gen = Q out
76133.8022+ 27835978.44+ 33835.62912 = 266386.4824 (T0-25)
266386.4824 (T0-25) = 27945947.87
27945947.87
T0 = + 25 = 129.9075 o C
266386.4824
TABLE NO 6.16
Q in 76133.8022 Q out 27945939.91
Qw 27835978.44
QD 33835.62912
27945947.87 27945939.91
6.13: ACID COOLER 1
Inlet acid temperature = 129.9075 o C

Outlet acid temperature = 30oC
90
Inlet water temperature = 20oC

Outlet water temperature =75oC
Assuming no heat loss, making a heat balance;
 163648.7289 × 1.465 × (129.9075 - 30) = m × 4.187 × (75 -20)
23952362.34
 m water = = 104011.8216 Kg
230.285
6.12: INTERPASS ABSORBER CIRCULATING TANK ( TANK 1)
100% H2SO4 at
132.04oC
A1 R
P W1 at 30oC
T (129.907 oC )
S
30.0624
Figure 6.12: INTERPASS ABSORBER CIRCULATING TANK ( TANK 1)
Q in = 230087.7302 × 1.4435× (132.04 -25) = 35551370.59 KJ
Q w = 2407.350461 × 4.187× (30-25) = 50397.87225 KJ

91
Q gen = heat of dilution = 9.304 × 2407.350461 = 22397.98868 KJ
98% H2SO4 = 18185.04753 × 1.465 × (129.9075 - 25) = 2794850.635
97% H2SO4 = 224255.115 × 1.4865 × (30.0624 - 25) = 1687577.508
Q out = 474935.2432 × 1.465 × (T0-25) = 695780.1313 (T0-25)
Making a steady state heat balance of the tank
Q in + Q w + Q d = Q out
 35551370.59 + 50397.87225 + 22397.98868= 695780.1313 (T0-25)
 92289.48375(T0-25) = 4080703.265
 T0 = 82.644 0 C
TABLE 6.12
Q in 35551370.59 Q out 40107758.62
Q WATER 50397.87225
98% H2SO4 2794850.635
97% H2SO4 1687577.508
Heat of generation 22397.98868
Total 40107790.28 Total

40107758.62
6.17: Acid Cooler 2
Inlet acid temperature = 82.6443oC

Outlet acid temperature = 30oC
Inlet water temperature = 20oC
92
Outlet water temperature =75oC (Assumed)
Q acid out = (474935.2432×1.465× (82.6443-30) = 36628857.97KJ

Assuming no heat loss, making a heat balance;
36628857.97
 m water = = 104011.3011kg
4.187(75−20)
Overall Heat Balance
( Input + Generation/ absorption )

KJ
Sulphur(S) 48680.5 98% H2SO4 305200.1
Oxygen (O2) 128189.62 from Tank 1
Nitrogen (N2) 474436.77
Water(H2O) 174437.61
Generation: Nitrogen (N2) 6238640
Dryer 21290.506
Melter 1212127.8 Oxygen (O2) 487005.8
Burner 142607806
Fuel 134322.64 Sulphur

dioxide
2289.86225
(SO2)
Reactor
Stage 1 30086089
Stage2 7466722.7
Stage3 1745670
93
Stage4 1258938.2
Absorber 1 30521530
Tank 1 22397.989
Absorber 2 23638147
Tank2 33835.629
Absorption
WHB1 -91548171
WHB2 -25017900
Eco1 -14132851
Eco2 -41261342
Cooler 1 -36628858
Cooler2 -23952362
Total 7033137.55 Total 7033136
Overall heat loss = 7033137.55-7033136= 1.55 KJ

94
Chapter 9
Design of Equipments
9.1 Design Of Storage Tank:
Aim:- To design a storage tank for 100% H2SO4 storage tank
Let us assume a capacity of 12,000 MT
Density of 100% H2SO4 = 1.8255 g/cc
In case of storage tank storing liquid, the pressure exerted by the liquid is not uniform. It
is the highest at the bottom and it gradually decreased towards the top of the vessel Therefore
while designing a process vessel the thickness is highest at the bottom and it gradually decreases.
 Optimum tank proportion
Let D = Diameter of the vessel
H = Height of the vessel

95
V = Volume of the vessel = πD2/4(H)m3
∴ H = 4V/πD2………………………………………………………………… (9.1)
A1 = Area of the shell = πDH
A2 = Area of the shell bottom = πD2/4
C1 = Annual cost of fabricated shell Rs/m2
C2 = Annual cost of fabricated bottom Rs/m2
C3 = Annual cost of fabricated roof Rs/m2
C4 = Annual cost of the installed foundation under the vessel Rs/m2 of tank bottom area
C5= Annual cost of the land in the tank area chargeable to the tank, Rs/m2 of tank bottom area.
Then, C = A1C1+ A2 (C2+C3+C4+C5) ……………………………………………………(9.2)
Simplifying the equation by substituting for H in terms of D, We obtain:
C = 4VC1/D+πD2/4[C2+C3+C4+C5] ………………………………………………… (9.3)
For minimum cost the slope of the curve of cost Vs. the diameter of the vessel, to contain the
fixed volume, V, must be equal to zero (dC/dD = 0). Therefore,
dC/dD = - 4VC1,/D2+πD/2 [(C2+C3+C4+C5)] = 0
Solving for D we obtain
D3 = 8V/π [C1/( C2+C3+C4+C5)] ……………………………………………………….. (9.4)
Solving for the volume, V we obtain
D3 = 8/π x (πD2H/4) x C1/( C2+C3+C4+C5)
Or, D = 2H x C1/( C2+C3+C4+C5) ………………………………………………………. (9.5)
 Tank having shell thickness dependent upon D and H

96
Tank having height and diameter such that the quantity D (H+1) exceeds 1720 ft 2 Butt welded
shells are 1515 ft2 for lap welded shells have shell thickness Which are depend upon D and H the
cost of the shell per unit area C1 is a function of D and H and for purpose of proportioning may
be assumed to be directly proportional to the shell thickness as follows:
C1 = C6 (H-1) D ………………………………………………………. (9.6)
C6 = C1/(H-1) D ……………………………………………………… (9.7)
Where C6 – proportionality constant
Substituting the value for C1 in equation (9.3), we get
C = 4V[C6(H-1)D]/D + π D2/4 ×( C2 + C3 + C4 +C5 ) …………………………(9.8)
Expanding and substituting for H
C = 4VC6 (4V/πD2) – 4VC6 + πD2/4 × (C2 + C3 + C4 + C5 )
Differentiating and setting equal to zero gives –
dC/dD = -32C6V2/πD3 – 0 + 2πD/4 × (C2 + C3 + C4 + C5 )= 0
or, πD/2 × ( C2 + C3 + C4 + C5 ) = 32C6V2/πD3
Substituting for V and C we obtain
Or, πD / 2 ×( C2 + C3 + C4 + C5 ) = 32C1 / [(H-1)D4]×[ π 2D4H2/16]
Since (H-1) for large tank is approximately equal to H, therefore
D (C2 + C3 + C4 + C5) = 4C1H
Or, D = 4H [C1/(C1 + C2 + C4 + C5)……………………………………(9.9)
Case-I: Let the tank is a small tank when shell, bottom and roof costs per unit area are
independent of diameter and thickness.
Assumptions:
97
(1) D/H = 0.3125 H

(2) Vessel is made of IS: 2004-1962 Grade low carbon alloy steel.
(3) The joints are double welded Butt joints.
Calculations:
D=0.3125H
4V 4 × 6573.54
∴H= 2 =
πD ¿¿
Or, H = 29.92 m = 98.16 ft
D = 9.35 m =30.68 ft
NowD(H-1) = 30.68×(98.16-1) ft2for butt welded joints.Thereforethe assumptions of small

storage tank cannot be accepted.
`Case-II
Let the tank is large one i.e.; when the fabricated shell cost per unit area is dependent on the
thickness and height. Under these conditions:-
D(H-1)¿1720 ft2
Assumptions:
D
1. = 0.625 H
H
2. The vessel is made of IS:2009-1962 2B grade low Carbon alloy steel.
3. The joints are double welded Butt joints
Calculations:
D = 0.625H
H = (π ×6573.54)
¿¿
98
Or, H = 27.77 m = 91.12 ft
D = 17.36 m = 56.94 ft
Now D(H-1) = 5131.4328 ft2 ¿1720 ft2
So the case II can be accepted.
Now from code book for unfired pressure vessels for IS:2004-1962 class 2 grade low
carbon alloy for temperature limits of 250℃.
Allowable stress, S = 12.1 kg/mm2
= 1210 kg/cm2
For double welded butt-joint, the joint efficiency factor E = 0.85
If allowable stress ‘S’ is in kg/cm2 minimum thickness of shell plates is given by
t = 50(H-0.3)DG/SE
Now
G=1.8255 ∴The thickness of the

first shell course (bottom layer),
t = 50(27.77-0.3)×17.36×1.8255/(1210×0.85)
= 42.32 mm
The standard thickness available close to 42.32 is 43
Let the height of each course be 2.5m ∴

Number of each course = 27.77/2.5 =11.108 ≈ 12
If 12 plates are used in each shell layer the number of vertical joints will be 11
Length of each plate = πD-(n × 3 ×10-3) = (π × 17.36)-(12× 3 × 10-3)
= 5.45 m
∴ Length of the plate = 6 m
∴ Size of the plate selected is 6006 mm × 2500 mm
The height up to which plates of lesser thickness can be used,

99
H = 1210× 0.85 × t / (50 × 17.36 × 18255) + 0.3
Or, H = 0.06491t + 0.3
Therefore, the thickness of the second shell course,
50×(27.77−0.3−2.5)×17.36 × 1.8255
t=
1210 ×0.85
=38.63 mm
Taking corrosion allowance,
tc = 38.63+0.3 mm
=38.93 ≈ 39 mm
Thickness of the third shell course,
50×(27.77−0.3−2× 2.5)×17.36 × 1.8255

t=
1210 ×0.85
= 35.24 mm
tc= 35.24+0.3
= 35.54 ≈36 mm
Thickness of the fourth shell course,
50×(27.77−0.3−3 ×2.5)× 17.36× 1.8255

t=
1210 ×0.85
= 31.69 mm
tc=31.69+0.3 mm
= 31.99 ≈ 32 mm
Thickness of the fifth shell course,
50×(27.77−0.3−4 × 2.5)×17.36 × 1.8255

t=
1210 × 0.85
100
= 28.15 mm
tc= 28.15+0.3 mm
= 28.45 ≈ 29 mm
Thickness of the sixth shell course,
50×(27.77−0.3−5× 2.5)× 17.36× 1.8255

t=
1210 ×0.85
= 24.60 mm
tc= 24.6+0.3 mm
=24.9 ≈25 mm
Thickness of the seventh shell course,
50×(27.77−0.3−6 ×2.5)× 17.36 ×1.8255

t=
1210 ×0.85
= 21.06 mm
tc= 21.06+0.3 mm
=21.36 ≈22 mm
Thickness of the eight shell course,
50×(27.77−0.3−7 ×2.5)× 17.36 ×1.8255

t=
1210 ×0.85
=17.52 mm
tc= 17.52+0.3 mm
= 17.83 ≈ 18 mm
Thickness of the ninth shell course,

101
50×(27.77−0.3−8 ×2.5)× 17.36 ×1.8255

t=
1210 ×0.85
= 13.97 mm
tc= 13.97+0.3 mm
= 14.27 ≈ 15 mm
Thickness of the tenth shell course,
50×(27.77−0.3−9 ×2.5)× 17.36 ×1.8255

t=
1210 ×0.85
= 10.43 mm
tc= 10.43+0.3 mm
=10.73 ≈ 11 mm
Thickness of the eleventh shell course,
50×(27.77−0.3−10× 2.5)× 17.36× 1.8255

t=
1210 ×0.85
= 6.89 mm
tc = 6.89+0.3 mm
=7.19 ≈ 8 mm
Thickness of the twelfth shell course,
50×(27.77−0.3−11 ×2.5)× 17.36 ×1.8255

t=
1210× 0.85
= 3.34 mm
Since the minimum standard thickness is 6 mm, the thickness of the 12 th shell plate will be equal
to the standard value of 6 mm.
102
The storage tank is designed for 12 courses each of 2.5 mm width and 11number of plates. For
each joint 3 mm excess thickness is allowed and 0.3 mm extra thickness is provided on each
plate for corrosion allowance.
Therefore Actual height = 12×2.5+0.0003×11
= 30.0033 m
Circumference of the vessel = π × D
= 54.54 m
D = 18.76 m
Actual capacity of the storage tank = (π /4 ¿ D2 H
=8293.2464 m3
Summary of storage tank design
Capacity = 8293.2464 m3
Diameter = 18.76 m
Height =30.0033 m
No of shell courses = 12
No of plates in each shell = 11
Length of each plate =6000 mm
Width of each plate = 2500 mm
Thickness of plates in each shell courses starting from bottom
First plate, t1 = 43 mm
103
Second plate, t2 = 39 mm
Third plate, t3 = 36 mm
Fourth plate, t4 = 32 mm
Fifth plate, t5 = 29 mm
Sixth plate, t6 = 25 mm
Seventh plate, t7 = 22 mm
Eight plate, t8 = 18 mm
Ninth plate, t9 = 15 mm
Tenth plate, t10 = 11 mm
Eleventh plate, t 11 = 7 mm
Twelfth plate, t12 = 6 mm
Material of construction IS: 2002-1962 2B
9.2 Design Of Heat Exchanger
Basis: 1 hour operation
474935.2432 kg of 98% H2so4 is to be cooled from 82.642℃ to 30℃.
Heat required to be removed:
Q = m H2SO4× Cp×(82.642-30)
=474935.2432× 1.465× (82.642 -30)
= 36627257.67kJ
Amount of cooling water required (supplied at 20℃ and heated to 75℃)

104
Q 36627257.67
mH2o = = =159051.8604kg
C p H 2 OX (40−25) 4.187 ×(75−20)
It is seen that large quantities of acid and cooling water cannot be handled by a single heat
exchanger.
∴They are divided into six streams.
474935.2432
Quantities of acid handled by a single stream =
6
= 79155.8739kg= 174508.8186lb
Heat to be removed
Q= 79155.8739×1.465×(82.642-30) = 6104542.948kJ
= 1458393.365kcal
= 5783550.568Btu
6104542.948
Quantity of water required =mH2O =
4.187 ×(75−20)
= 26508.64341kg
= 58441.55107lb
Stream 2, t2 (167℉ )
Stream 1, T2 (86℉
Stream 1, T1 )
(180.7556℉ )
Stream 2, t1 (68℉ )
105
Fig 9.1: The Heat Exchanger E – 1
T1 = 180.7556oF
T2 = 86oF
t2=167oF
t1 = 68oF ∆ t=13.7556=13.7556 ℉
∆ T =18 ℉
Fig 9.2: Temperature Profile
18−13.7556
LMTD = =15.783℉
ln ⁡(18 ÷ 13.7556)
Assuming a design coefficient of 200 Btu/hrft 2℉ (inclusive of dirt factors) (Ref. Alfalaval
brochure for Sulphuric acid coolers)
Q 5783550.568
Area required = A = = =1832.209ft2
U D × LMTD 200× 15.783
Since, the required area is greater than 200ft2 we will use a shell and tube heat exchanger.
106
We choose 18 BWG, ¾ inch Outer Diameter (OD), 0.625inch inner diameter (ID) tubes of
length 16 ft of 1 inch square pitch. (Ref. to data from Table: 10, Process Heat Transfer, D.Q
Kern)
Area of a single tube = π × D × L
3 1
= π× × ×16
4 12
= π ft2
1832.209
∴Number of tubes required =
π
= 583.22
Referring to data from Table: 9, Process Heat Transfer, D.Q Kern
For 584 tubes in 4 passes we have a corresponding shell ID of 31 in (Ds)
2-shell passes with shell Inner Diameter (ID) = 31 in
4-tube passes with 584 tubes
Minimum baffle efficiency = 31/5
= 6.2
Clearance, C’ = pitch – OD
= 1-(3/4) = 0.25inch
Table 9.1 ∆t (actual temperature difference)
Hot fluid (℉) Cold fluid (℉) Diff (℉)

180.7556 (T1) Higher temp 167 (t2) 13.7556
86 (T2) Lower temp 68(t1) 18
94.7556 Difference 99 4.244
107
180.7556−86
R = (T1-T2)/ (t2-t1) = = 0.9571
167−68
167−68
S= (t2-t1)/ (T1-t1) = = 0.872
180.7556−68
From fig19, D.Q.KERN
LMTD correction factor FT = 0.85
∆t = FT×LMTD = 0.85 ×15.783 = 13.42℉
Since the temperature differences are not very large, the average temperatures are used for
calculations.
180.7556+86
Ta = = 133.38℉
2
167+68
ta= = 117.5℉
2
Here sulphuric acid being more corrosive is passed through the tubes and water through the shell
side.
Shell side (H2O) Tube side (H2SO4)

108
1 For ¾ in OD, 18 BWG, tube flow area for a

As = 31×0.25×6.2 ×
144
single tube
= 0.334 ft2
at’ = 0.334 in2
at = (Nt× a t ’)/ (144× n)

58441.55617
Gs =
0.334
= 175142.5068 584 ×0.334
=
144 × 4
=0.3386
At ta = 117.5℉
174508.8186
µ = 1.58 lb/fthr Gt=
0.3386
=515383.398 lb/hrft2
k = 0.356Btu/hrft ℉/ft
2
D = 0.652 in = 0.652/12 = 0.054ft

cp = 1 Btu/lb℉
At Ta = 133.38℉
0.95
De = = 0.0792 (From fig 28, D.Q.KERN) µ = 22.022lb/fthr, cp = 0.36 Btu/lb℉
12
k = 0.21 Btu/hrft2℉ / ft
175142.5068× 0.0792
Res = 515383.398× 0.054
1.58 Ret = = 1263.8
22.022
= 11755.328
From fig 24, D.Q.KERN

From fig 28, D.Q.KERN
JH = 6.9
JH = 63
109
k C p ×µ 1/3 k C p × µ 1/3
ho =JH× ×( ) hi = JH× ×( )
De k D k
0.356 1× 1.58 1/3 0.21 0.36 × 22.022 1/3

= 63× ×( ) = 6.9× ×( )
0.0792 0.356 0.054 0.21
= 422.856 Btu/hrft2℉ = 90.02 Btu/hrft2℉
ID
hoi = hi×
OD
0.652
= 90.02× = 78.408 Btu/hrft2℉
0.75
Table 9.2 Determination of h0 and h0i for shell side and tube side
hoi × h0
Clean overall coefficient, UC =
h oi +h 0
422.856 ×78.408
= = 66.14 ≅66.1 Btu/hrft2℉
422.856+78.408
Design overall coefficient (UD)A = 584×16 × 0.1963 = 1834.2 ft2
5783550.568
UD = = 54.96 Btu/hrft2℉
1834.2×13.42
(U C – U D )
Dirt factor, RD =
UC× U D
= 0.0031 hrft2℉/Btu
Which is well within limits for untreated cooling tower and artificial spray pond water? (0.003
hrft2℉/Btu Table12 DQ KERN)
Table 9.3 Determination of Pressure drop in shell side and tube side
Shell side (water) Tube side (H2SO4)

Re = 11755 Re = 1263
110
f = 0.002 ft/inch (fig 29 D.Q.KERN) f = 0.0005 ft2/in2 (fig 26 D.Q.KERN)
12× L D = 0.0543 ft
No. of crosses = N+1 =
B
S ( specific Gravity)=1.84
12×16
= = 45.17 ≅
4.25
f ×G 2t × L× n
46 ∆Pt =
5.22×10 10 × D × S × Ø 1
Which is 46×2 = 92 for two passes

0.0006× 515383.32 × 16 ×4
=
5.22×10 10 ×0.0543 × 1.84 ×1
Ds = 31/12 =2.58 ft
S ( specific Gravity) = 1
= 0.16 psi
For Gt=515383.3
f ×G 2s × D s( N + 1)
∆Ps=
5.22×10 10 × D e × S × Ø s
V2/2g = 0.036 [fig 27 D.Q.KERN]
=
4n V2
∆Pr= ×
0.002×(175142.5)× 175142.5× 2.58 ×92 s 2g
5.22×10 10 ×0.0792 ×1 ×1 4×4
= ×0.036
1.84
= 0.313 psi
= 3.5 psi
∆PT = ∆Pt + ∆Pr
= 0.16 + 0.313
Allowable ∆ P s = 10 psi
= 0.473 psi
Allowable ∆Pt = 10 psi
111

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listing is likely to be incomplete or include aggregate categories. A common description of

Fig 1.2: Global Sulphuric Acid Demand by Application (Source:

Properties and Uses of Sulphuric Acid

2.1 Physical Properties Of Sulphuric Acid

properties of sulphuric acid are tabulated:

Color Colorless , water-white

Standard Enthalpy Of Formation -8.305KJ/ Kg

Table 2.1 Physical Properties of H2SO4

heavy chemicals, petrochemicals, fertilizers, super phosphates and ammonium sulphate

Standard strengths available in the market are listed below:-

SPECIFIC GRAVITY -1.250 33.33%

Table: 2.2 Standard Strengths of H2SO4

2.2 Chemical Properties of Sulphuric Acid

 Sulphuric acid is a diprotic acid (can donate 2 protons to a base)

 Sulphuric acid ionizes in water in two stages:

H2SO4(l) + H2O(l) HSO4-(aq) + H3O+(aq)

HSO4-(aq) + H2O(l) SO42-(aq) + H3O+(aq)

 Sulphuric acid is a strong acid (complete dissociation in water, Ka approaches infinity)

 Sulphuric acid reactions:

 sulphuric acid + metal metal sulfate + hydrogen gas

 sulphuric acid + carbonate metal sulfate + carbon dioxide gas + water

 sulphuric acid + base salt + water

 sulphuric acid + ammonia ammonium sulfate

 Sulphuric acid can take part in redox reactions.

2.3 Applications of Sulphuric Acid

accomplished by simple scrubbing operation.

quantities are major ingredients of the household detergents and lubricants.

3.1 A Brief History

3.2 Commercial Methods of Preparation

Brief Description of DCDA Process

4.1 Raw Materials and Products

CO2, SO3 gas. It is obtained:

 By burning molten waste elemental sulphur (~70% of world production)

 From high SO2 strength metallurgical off-gases (~20%)

 By decomposing spent (used) sulphuric acid catalyst (~10%).

beneficially removes SO2 from smelting and roasting off-gases.

4.2 Manufacturing Process

Sulphuric acid manufacturing consists of the following steps:

1. Gas cleaning and gas drying

2. Generation of sulphur dioxide

3. Catalytic oxidation of sulphur dioxide to sulphur trioxide

4. Absorption of sulphur trioxide

1. Gas Cleaning and Gas Drying

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

2. Generation of Sulphur dioxide

reaction involved is:

S (l) + O2 (g) SO2 (g) ΔH= -298 kJ/mole,25˚C

3. Catalytic Oxidation of Sulphur dioxide to Sulphur trioxide

Oxidation of S02 to S03 is accomplished in multi-stage, fixed-bed catalytic converters equipped

Fig 4.1: Photograph of catalyst pieces, courtesy Haldor Topsøe A/S

4. Absorption of Sulphur trioxide

The reaction is:

SO3 (g) + H20 (l) H2SO4 (l) ΔH= -130 kJ/mole,25˚C

large amount of H2SO4 absorbs heat of reaction.

oleum tower may be placed before the intermediate absorber.

used in acid piping and coolers.

Kinetics and Thermodynamics of the Process

5.1 Reaction kinetics and Thermodynamics

dry SO2 gas down through horizontal beds catalyst.

temperature, total pressure, and concentrations (partial pressures) of the reactants.

and temperature was developed empirically by Bodenstein and Pohl.

The relation is given as