CHAPTER 1

1.0 INTRODUCTION TO DESIGN

1.1 BACKGROUND OF STUDY
Sulphuric acid is a mineral acid composed of elements like Sulphur, oxygen and hydrogen, with
the molecular formula H2SO4. It is a colorless, odorless and viscous liquid that is miscible with
water. Pure Sulphuric acid does not exist naturally on Earth due to its strong affinity to water
vapor; for this reason, it is hygroscopic and readily absorbs water vapor from the air.
(“Sulphuric acid safety data sheet, 2015”). Sulphuric acid is produced from Sulphur. Sulphur
dioxide is first obtained by the burning of the molten Sulphur in presence of air. Sulphur dioxide
is then converted to Sulphur trioxide in presence of vanadium pentoxide catalyst. The Sulphur
trioxide thus obtained is absorbed in recycling concentrated Sulphuric acid in an absorption
tower. The plants installed earlier, and the smaller units of Sulphuric acid plants use a single
absorption process which has conversion efficiency of 96–98%.

Sulphuric acid has different qualities depending on its concentration. Sulphuric acid will
degrade anything from tissues (e.g., skin and flesh), metals, and stones when it comes into direct
contact with them, while a higher acidic concentration can cause corrosion. The acid in
concentrated form has severe dehydrating and oxidizing characteristics. According to the
Encyclopedia Britannica, heating causes partial breakdown of pure acid into water and Sulphur
Trioxide, with Sulphur Trioxide leaving as vapor, until the acid concentration falls to 98.3%.

Although Sulphuric acid is non-flammable, contact with metals in the event of a spillage can
lead to the liberation of hydrogen gas. The dispersal of acid aerosols and gaseous Sulphur
dioxide is an additional hazard of fires involving Sulphuric acid. Sulphuric acid is not
considered toxic besides its obvious corrosive hazard and the main occupational risks are skin
contact leading to burns and the inhalation of aerosols. High-concentration aerosol exposure
causes fast and severe irritation of the eyes, respiratory tract, and mucous membranes, which
subsides quickly after exposure, while there is a danger of pulmonary edema if tissue damage
is severe. At lower concentrations, the most reported symptom of chronic exposure to Sulphuric
acid aerosols is tooth attrition, which has been observed in almost all studies; indications of
possible chronic pulmonary injury are equivocal as of 1997. The permissible exposure limit
(PEL) for Sulphuric acid in the United States is 1 mg/m3. Sulphuric acid consumption has been

1
linked to vitamin B12 insufficiency, which has been linked to subacute degeneration. In such
circumstances, the spinal cord is most damaged, but the ocular neurons may also show
demyelination.

Sulphuric acid is arguably one of the most produced industrial chemicals in the world. Its
applications have a wide range- from the manufacture of fertilizers, pigments, dyes, drugs,
explosives, detergents, and inorganic salts and acids to petroleum refining and metallurgical
processes, electrolyte in lead–acid storage batteries etc.

1.2 Why is Sulphuric acid produced?

Sulphuric acid is a vital commodity chemical, and a country's output of the chemical is a reliable
measure of its industrial strength. The "wet method" for producing phosphoric acid, which is
used to make phosphate fertilizers and trisodium phosphate for detergents, is where Sulphuric
acid is used the most (60 percent of total production worldwide). In the chemical industry,
Sulphuric acid is utilized for a variety of various uses. It's the most common acid catalyst for
converting cyclohexanone oxime to caprolactam, which is used to make nylon. It's utilized in
the Mannheim process to make hydrochloric acid from salt. H2SO4 is widely used in petroleum
refining, for example, as a catalyst in the reaction of isobutene with isobutylene to produce
isooctane, a chemical that boosts gasoline's octane rating (petrol). Sulphuric acid is used to make
dyestuff solutions and is the "acid" in lead-acid batteries (car) batteries. It is also used as a
general dehydrating agent in its concentrated form. It is widely used in metal processing for
example in the manufacture of copper and the manufacture of zinc and in cleaning the surface
of steel sheet, known as 'pickling', prior to it being covered in a thin layer of tin, used to make
cans for food.

1.4 Aim and objectives

1.4.1 Aim

To produce 10,000litres/day of Sulphuric acid from Sulphur

1.4.2 Objective

To achieve 99% purity by using the Double Contact Double Absorption (DCDA) contact
process

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 CHAPTER 2

2.0 LITERATURE REVIEW

2.1 Definition of Sulphuric acid

Sulphuric acid is a strong mineral acid with the molecular formula H2SO4. Sulphuric also
spelled Sulfuric (H2SO4), is also called oil of vitriol, or hydrogen sulphate, is a dense, viscous,
colorless, oily, corrosive liquid; one of the most commercially important of all chemicals.
Sulphuric acid is prepared industrially by the reaction of water with Sulphur trioxide, which in
turn is made by chemical combination of Sulphur and oxygen either by the contact process or
the chamber process. In various concentrations the acid is used in the manufacture
of fertilizers, pigments, dyes, drugs, explosives, detergents, and inorganic salts and acids, as
well as in petroleum refining and metallurgical processes. In one of its most familiar
applications, Sulphuric acid serves as the electrolyte in lead–acid storage batteries.

Table 2.1 Attributes of Sulphuric acid

Attribute

Alternate names Oil Of Vitriol, Hydrogen Sulfate

General appearance/qualities dense, clear (colorless), oily, corrosive liquid

Specific gravity (25° C) 1.83 (Pure Sulphuric acid)

Freezing point 10.37° C (Pure Sulphuric acid)

Boiling point 338° C (98.3% conc. acid at 1 atm)

Commonly supplied concentrations 78%, 93%,98%

Related solutions Oleum (Fuming Sulphuric acid)

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2.2 History and Current processes
Earliest days: From in the 16th century, records of a substance like Sulphuric acid in its most
rudimentary form began to emerge. The general information acquired throughout the literature
survey about how Sulphuric acid became what it is today points to Johann Van Helmont, who
used destructive distillation of green vitriol (Ferrous Sulphate) and Sulphur burning to create
what was then known as 'Oil of Vitriol.'

Beginning of Industrial scale production: Sulphuric acid was primarily produced in the 1790s
for the Leblanc process of producing Sodium Carbonate. In the 17th century, Johann Glauber
pioneered the technology of Sulphur combustion with saltpeter (potassium nitrate) (History of
Sulphuric Acid, 2012). Whereas prior production had primarily been on a lab scale, it was
around this time that industry visionaries began to recognize the economic value of Sulphuric
acid. But Sulphuric acid's best days were still ahead of it.

Breakthrough: The development of the Lead Chamber Process by John Roebuck in the mid-
eighteenth century was a milestone in Sulphuric acid production because it allowed the industry
to increase production capacity while also being far more economically viable than any other
Sulphuric acid processes previously developed. Further advancements to the process were made
in the following decades, with enhanced Nitrogen Oxide recovery adding to the overall
development of the Lead Chamber Process.

Pinnacle: The evolution of Sulphuric acid production reached its climax in the beginning of the
19th century, where Phillips, in Bristol, England, patented the oxidation of Sulphur Dioxide into
Sulphur Trioxide 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 Sulphuric
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.

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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 (Lloyd, 2011).

 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
Sulphur Dioxide containing gases having moisture. Further the air used for oxidizing
Sulphur 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.

 Development of the ‘double’ catalyst process by Bayer in the 1960s: This led to higher
conversion of Sulphur Dioxide and reduction of fugitive emissions of Sulphur Dioxide. This
phenomenon involves adding the elementary Sulphur Trioxide absorption step ahead the
final catalytic stage. The introduction of environmental regulations during the period fueled
this development.

The discovery of Sulphuric acid is credited to the 8th century chemist and alchemist, Jabir ibn
Hayyan (Geber). The acid was later studied by 9th century Persian physician and alchemist Ibn
Zakariya al-Razi (Rhazes), who obtained the substance by dry distillation of minerals including
iron (II) sulfate heptahydrate, FeSO4·7H2O, and copper (II) sulfate pentahydrate, CuSO4·5H2O.
When heated, these compounds decompose to iron (II) oxide and copper (II) oxide, respectively,
giving off water and sulfur trioxide, which combine to produce a dilute solution of Sulphuric
acid. This method was popularized in Europe through translations of Arabic and Persian
treatises, as well as books by European alchemists, such as the 13th-century German Albertus
Magnus.

Sulphuric acid is produced using two major procedures (lead chamber and contact), and it is
sold in a variety of grades and concentrations. The older of the two procedures, the lead chamber
technique, is used to manufacture much of the acid used in fertilizer production; it produces a
somewhat dilute acid (62-78% H2SO4). The contact process creates a purer, more concentrated

5
acid, but it necessitates the use of purer raw materials and costly catalysts. Sulfur dioxide is
oxidized and dissolves in water in both processes. Sulphur dioxide can be produced by burning
sulfur, pyrites (iron sulphides), roasting nonferrous sulphide ores prior to smelting, or burning
hydrogen sulphide gas. Sulphuric acid can also be generated from waste ferrous sulphate
solutions from pickling iron and steel, as well as waste acid sludge from oil refineries.

2.3 Application and Uses

Sulphuric acid is a very important chemical commodity, and indeed, a nation’s Sulphuric acid
production is a good indicator of its industrial strength

 Production of Phosphoric acid: Commonly regarded as the main source of

consumption of Sulphuric acid, the "wet method" of producing phosphoric acid, is used
for manufacture of phosphate fertilizers. Rock phosphate or, fluorapatite, is treated with
93% Sulphuric acid to produce calcium sulfate, hydrogen fluoride (HF) and phosphoric
acid (Phosphoric Acid, 2013).

 Iron and steel manufacturing: Sulphuric acid is used to remove rust, scaling and other
forms of oxidation from rolled sheet and billets before being used for the manufacture
of automobiles and other appliances. Since disposal of spent acid and reacquisition of
fresh acid has been observed to be costly, most steel plants consist of spent acid
regeneration (SAR) units where spent acid is burnt with natural gas, refinery gas or other
fuel sources which produce Sulphur Dioxide and Sulphur Trioxide vapors, which are
then used to produce "new" Sulphuric acid. SAR units have been incorporated in metal
smelting plants, oil refineries, and other industries that require bulk quantities of
Sulphuric acid.

 Manufacture of Aluminum compounds: Also known as ‘paper maker’s alum’,

Aluminum Sulphate is produced in large scale in the paper making industry. Aluminum
oxides (Bauxites) are first purified into Aluminum soaps (Al (OH)3) on paper pulp
fibers. Adding Sulphuric acid gives gelatinous Aluminum carboxylates, which
coagulates the pulp fibers into a hard paper surface (THE MANUFACTURE OF
ALUMINIUM SULFATE). Also, Aluminum Hydroxide which is used as a coagulant
in water treatment plants is also manufactured from Sulphuric acid.

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  Manufacture of Ammonium Sulphate: An important nitrogen fertilizer, this is
produced in mass scale by reacting Ammonia with Sulphuric acid where Ammonia is
converted into Ammonium Sulphate which gets crystallized and is separated by
centrifugation or filtering (Gowariker, 2009). Ammonia being a byproduct in coking
plants is often supplied to iron and steel making plants along with coke to produce the
above as a byproduct, which is used as a form of disposal of waste Sulphuric acid. The
byproduct is then sold as an agro chemical.

Application as a catalyst:

Industry Uses

Petroleum refining Producing isooctane from isobutene and

isobutylene

Manheim process Conversion of salt into Hydrochloric acid

Nylon manufacturing industry Conversion of cyclohexanone oxime to

caprolactam

Other uses: Sulphuric acid is also an important component in the manufacture of dyes where
acidic media such as Sulphuric acid is used to ‘set’ the color of acid dyes that are used to dye
of silk, wool, nylon and modified acrylic fibers (ACID DYES). Pigments such as Titanium
Dioxide also employ Sulphuric acid to decompose and dissolve their raw deposits (Eg: Limonite
in the case of TiO2) (Titanium dioxide). Sulphuric acid is also used as the electrolyte in lead-
acid (car) batteries. It is also used as a general dehydrating agent in its concentrated form which
is used in detergents.

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2.4 Raw material sourcing

2.4.1 Availability of raw materials

The plant's capacity is limited by the availability of raw materials. Sulphur is the most common
raw material used in the production of Sulphuric acid, with the exception of those who create it
by recovering Sulphur oxides.

2.4.2 Different methods of sourcing Sulfur based compounds as raw material

Sulphur is mined in elemental form in volcanic areas or salt domes in buried sedimentary
regions associated with natural gas and crude oil deposits. According to Chemical information
Centre maintained online by the Department of Chemistry at University of York, Sulphur
recovered from oil and natural gas in the petroleum industry now accounts for about 70% of all
Sulphur used (Sulphuric acid - Feedstock). Thus interestingly, Sulphur can be procured both
upstream and downstream of petroleum refining- i.e., along with crude oil deposits or following
refining as Hydrogen Sulphide or as Alkyl Sulphides. Sulphur in this form is not only toxic but
has the tendency to poison catalysts. In any case, as far as using petroleum byproducts as a
source for Sulphur is concerned, the byproduct stream must be subject to processing to obtain
Sulphur in elemental form.
Sulphur can also obviously be sourced from metal deposits since some of them exist in the form
of Sulphides. Galena (Lead based) and Sphalerite (Zinc based) are both Sulphides and are
usually found together. They are mined in several countries including China, Australia, and
parts of North and South America. A considerable amount of Sulphur Dioxide is produced when
they are roasted during processing, which, due to the emergence of more stringent emission
controls, are now recovered as Sulphuric acid.
Moving on, Sulphuric acid is now being ‘regenerated’ in some plants which has been perceived
recently to be a better option than replenishing with fresh stocks and discharging spent acid.
All in all, the review of literature pertaining to sourcing of raw material indicated a growing
trend of sourcing Sulphur in the form of metal smelting vapor emissions, flue gas recovery,
recovery from oil and gas and recycling of the acid in situ, owing to strict controls on emissions,
rather than sourcing through direct mining.

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2.5 Existing process routes for Sulphuric acid production
There are two main processes for manufacture of Sulphuric 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 pointed out 3 different processes are based on the general
operating principle of the contact process.

1. Single contact process

2. Double contact process

3. Wet Contact Process (WCP)

2.5.1 Lead Chamber Process and its development

This was a crucial development in the development of viable production processes for Sulphuric
acid. John Roebuck and Samuel Gardner introduced a method to produce the Sulphuric acid in
lead lined chambers.

Typical steps and reactions of the lead chamber process are as follows (Lloyd, 2011).

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

Sulphur is oxidized by KNO3 and produces Sulphur Trioxide. 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 Sulfur Trioxide converts to Sulphuric 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 in 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 Sulphur Dioxide for produce Sulphuric 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.

2.5.2 Modern Lead Chamber Process

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

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

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

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

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

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

Nitrogen can also be provided in two ways:

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 Sulphuric acid. At that reactor SO2 is mixed and reacted with
Sulphuric 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 % Sulphuric 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.

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 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 Sulphur Dioxides
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 78-80% concentrated Sulphuric acid.

Figure 2.1: Process flow of the Lead Chamber Process

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

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Step 1 - The Sulphur should burn to form Sulphur Dioxide 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 HydroxynitroSulphuric acid

2 HOSO2.NO(OH) + O  2 HOSO2.NO2 + H2O

Step 4 - The Nitro Sulphuric acid isomerized

2 HOSO2.NO2  2 HOSO2.ONO

Step 5 - The Sulphuric acid formed by Nitro Sulphuric acid and Nitrous acid is formed as a
byproduct.

HOSO2.ONO+ H2O HNO2+ H2SO4

Step 6 – Alternative step 5.

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.

2.5.3 Contact process

The contact process is the current method of producing Sulphuric acid in the high
concentrations needed for industrial processes. Platinum was originally used as the catalyst for
this reaction; however, as it is susceptible to reacting with arsenic impurities in the Sulphur
feedstock, vanadium(V) oxide (V2O5) is now preferred

Development

In general, when considering the capacity more than a century since its development, we can
see expanded production plants which have over the 5000 metric tons per day are in the plants

13
with a global clientele. This increase can be attributed to the increasing demand for the
Sulphuric acid due to various aspects. Also, larger equipment, reduced gas strength and
increasing gas flow rates could well have affected this kind of improvement of the capacity in
the contact process (Friedman).

Contact process can be divided into the following main steps. Among these main steps, several
sub processes are used to optimize the manufacturing process.

1. Combining of Sulphur and oxygen.

2. Purifying Sulphur Dioxide in the purification unit.

3. Adding excess of oxygen to Sulphur Dioxide in presence of catalyst vanadium oxide.

4. High concentrated Sulphuric acid is added to Sulphur Trioxide, as a result Oleum is produced

5. Water is added to Oleum and 98% Sulphuric acid is formed.

Basic chemical reactions associated with this process are as follows.

• S(l) + O2(g) --> SO2(g)

• SO2(g) + ½ O2(g)  SO3(g) Δ = -99 kJ/mol

• SO3(g) + H2SO4(l)  H2S2O7(l)

• H2S2O7(l) +H2O(l)  2H2SO4(l)

A detailed account of the key stages in the contact process followed in Sulphuric acid plants is
given below (Louie, 2005).

STEP 1:SO2 Production and Purification: If purified elemental S can be obtained for our
process, first step involves spraying melted Sulphur into an excess of dry air at atmospheric
pressure. For this step, dry air is obtained by passing air through a Sulphuric acid bed, a
dehydrating agent. This is done to avoid acid mist and corrosion in downstream pipes. Since the
mixture of Sulphur Dioxide and air obtained may contain various impurities, which must be
removed; (otherwise, it will lead into catalyst poisoning and loss in efficiency) several
purification steps are followed which includes a dusting tower, cooling pipes, a scrubbing tower,
a drying tower, an arsenic purifier and testing box. During this purification, the mixture is

14
initially passed through an electric precipitator, consisting of a chamber with high electric
potential wires. The electric charge attracts solid particles present in the stream. Then gas
mixture is led to a water scrubber where it is completely freed from dust particles. It then dried
by a spray of concentrated Sulphuric acid in another chamber through arsenic purifier where
every trace of arsenic oxide is removed. During this first main step, an excess of air (Oxygen)
ensures the Sulphur reacts completely. The combustion of Sulphur generates a lot of heat. It is
necessary to cool the gas stream from 1000oC to around 450oC, the optimum temperature for
the next step. Heat exchangers are used to remove the excess heat and recycle this heat energy
so it can be used to re melt more Sulphur or power turbines for electricity.

STEP 2: Catalytic Oxidation of SO2 and SO3: Clean, dry Sulphur Dioxide is the feedstock
for this stage. This Sulphur Dioxide is mixed with purified air at pressure slightly higher than
atmospheric in a counter current manner, and is passed through a catalyst tower, called a
converter. The tower contains several layers (usually 3-4 as per referred literature) of loosely
packed Vanadium Pentoxide or Platinum on perforated shelves. The catalyst is placed in vertical
iron pipes inside the converter. The preheated mixture of Sulphur Dioxide and air form Sulphur
Trioxide (The Contact Process, 2013). Catalytic oxidation of SO2 is a reversible process, which
depends on several factors such as the correct catalyst, temperature, and pressure. Platinum was
formerly employed as a catalyst for this reaction but is now considered susceptible to poisoning
by arsenic impurities in the Sulphur feedstock and it is comparatively expensive, vanadium (V)
oxide (V2O5) is now highly preferred in commercial productions. K2O may be used as a
promoter to enhance the activity of the catalyst. The mechanism for the catalytic action occurs
in two steps:

Step 1: Oxidation of SO2 into SO3 by V5+:

2 SO2 + 4V5+ + 2 O2- 2 SO3 + 4V4+

Step 2: Oxidation of V4+ back into V5+ by oxygen (catalyst regeneration):

4 V4+ + O2 → 4 V5+ + 2 O2-

Several factors are considered when considering the optimum pressure and temperature for this
catalysis Equilibrium Considerations: To maximize the yield the following measures are
adopted:

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 Supply of excess oxygen

 Apply high pressure (due to 1.5:1 ratio)

 Apply low temperatures (as reaction is exothermic)

Kinetic Considerations: Deals with catalytic usage, application of high temperature and
pressure.

Energy Considerations: Minimizing energy use (thus cost) includes dealing with the following.

 Applying atmospheric pressure (as high-pressure containers are expensive)

 Optimizing use of catalysts, or justifying if catalysts are needed as cost of researching,

producing, and using them are high

 Heat recovery from exothermic reactions (combustion of Sulfur)

According to the Le Chatelier's principle, at a lower temperature, a high pressure should be used
to shift the chemical equilibrium towards the right, hence increasing the percentage yield.
However, too low temperatures also are not recommended, as it will lower the formation rate
to an uneconomical level. Hence to increase the reaction rate, high temperatures (450 °C) are
maintained in the gas streamline by the heat exchangers in the previous processing section.

High pressure would favor the forward reaction. Data gathered from literature points out that it
is not possible to build acid resistant towers, which can withstand high pressures. A pressure of
760 - 1520 mm of Hg is used. Excess of oxygen is necessary, as it would favor the forward
reaction. Thus, a 5:1 air: SO2 ratio is used (essentially 1:1 O2:SO2) creating an excess of oxygen.
While maintaining above conditions and in the presence of vanadium pentoxide, a conversion
rate of 96% can be obtained by this process, according to literature.

STEP 3: Absorption of SO3: The Sulphur Trioxide from the final catalyst bed is dissolved in
98% Sulphuric acid in the absorption tower. The acid is sprayed over the SO3 and produces an
oily liquid called Oleum. This is preferable over directly dissolving Sulphur trioxide in water as
this forms Sulphuric acid mists, due to the large heat of dissolution (130 kJ/mol), which are hard
to control and difficult to coalesce. In addition, it is difficult to separate the Sulphuric acid gas
from others such as nitrogen once it is produced in gaseous form.

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STEP 4: Conversion of Oleum to H2SO4: In dilution tanks, water is mixed with Oleum to
produce 98% Sulphuric acid (18M). Oleum is reacted with water to form concentrated H2SO4.
The average percentage yield of this reaction is around 30%. It is sold either as concentrated
(98%) or diluted acid.

Figure 2.2: Process flow diagram of contact process

2.6 Process selection

Comparison between the Lead Chamber Process and the Contact Process

In terms of Economics

Product quality and concentration: The concentration of the final product from the contact
process is about 98% Sulphuric 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 throughout, quality and concentration of the acid
produced with respect to the Contact Process. Currently most end uses of Sulphuric acid are for
the high concentrated form. Thus, in terms of product capacity and concentration, the contact
process is a more attractive option.

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

17
significant portion of this. For the contact process the high pressures favor 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 is lower than what could have been expected.

Energy consumption: Energy consumption for Sulphur burning is same for both lead and
contact process because in our case elemental Sulphur will be procured to produce Sulphur
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 requires more energy for
burning of KNO3. The burning step is in any case, the main energy consuming step. In the
modern lead chamber process, SO2 is sent to the glower tower. That means the initial step of
both processes is same. In addition to this though, 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 because the contact process is compact and less of gas circulation needs
than the lead chamber process and this matter because more gas conveying requires 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- Sulphur 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

18
however, modern lead chamber process also sends SO2 to the glower tower which can balance
out the energy consumption.

In terms of safety

Production of Sulphur Dioxide is a key step in both processes. Fugitive emissions amounting to
impressible levels or process hazards resulting in major leaks of SO2 would compromise the
health of factory personnel and even beyond. The environmental impact of oxides of Sulphur
are thus common in both cases. In addition, however, the lead chamber process 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.

Optimum process selection for Sulphuric acid should incorporate process and economic realities
with minimum risk and minimum footprint on the environment. Considering the above
comparison of the two processes the contact process has more advantages in terms of its
relative advantages in terms of operations economics, energy and safety issues elaborated
earlier. 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)

19
● Wet Contact Process (WCP)-This is not widely used in large scale due to Sulphuric acid mist
generation in the absorption of the SO3 to H2O directly

2.6.1 Processes under contact process

SCSA: The single contact single absorption process is the older (of the two) process in the
chemical industry among Sulphuric production plants where the contact process had been
implemented. A single contact, single absorption system for oxidizing Sulphur dioxide to
produce Sulphuric acid comprising: an inlet for a gas supply comprising Sulphur dioxide and
oxygen; a series of contact catalyst beds comprising one or more vanadium oxide catalyst beds
fluidly connected in series to the gas supply inlet and one or more platinum catalyst beds fluidly
connected in series to the last vanadium oxide catalyst bed in the series of vanadium oxide
catalyst beds, wherein each of the contact catalyst beds comprises an inlet and outlet; a platinum
catalyst bed heat exchanger with one side connected between the outlet of the last vanadium
oxide catalyst bed in the series and the inlet of the first platinum catalyst bed in the series; an
absorption tower with an inlet fluidly connected to the outlet of the last platinum catalyst bed in
the series; and a Sulphur trioxide heat exchanger with one side connected between the outlet of
the last platinum catalyst bed in the series and the absorption tower inlet. In comparison with
other forms of the contact process, the single contact single absorption process holds more heat
of the gas than the double contact double absorption process. The reason for this phenomenon
is that the heat losses are less due to the absence of intermediate absorption process prior to the
main absorption unit. The SCSA also results in the flue gas downstream of the main absorption
tower containing more Sulphur Dioxide, since the trace amounts of SO2from the converter has
not been captured with an intermediate system. The SCSA process exists in modern plants to
process Sulphur Dioxide gases with low content (3%-10% SO2) or where the content of Sulphur
Dioxide varies widely regardless of the range. The disadvantage of the SCSA process lies in the
fact that the maximum SO2 conversion is about 98%. By adding a second SO3 absorber and one
or two catalysts beds, 99.5% - 99.9% conversion efficiency can be achieved. The DCDA process
can thus achieve higher conversion than the SCSA process (Riegel & Kent, 2003).

DCDA: The principle behind the Double Contact Double Absorption system is based on the
observation that if the product stream with gases (SO2) and (SO3) is passed through absorption
towers twice, the unconverted SO2 in the product stream from the converter can be reduced,

20
resulting in the production of higher-grade Sulphuric acid. The SO2-rich gases reach the
catalytic converter and are transformed to SO3 in a DCDA system, completing the first stage of
conversion. Both SO2 and SO3 are present in the exit gases from this step, which are passed via
intermediary absorption towers, where Sulphuric acid is dripped down packed columns and SO3
combines with water, raising the concentration of Sulphuric acid. Even though SO2 passes
through the tower, it is unreactive and exits the absorption tower. This stream of gas containing
SO2 is passed through the catalytic converter bed column again achieving up to 99.8%
conversion of SO2 to SO3 and the gases are again passed through the final absorption column
thus resulting not only achieving high conversion efficiency for SO2 but also enabling
production of higher concentration of Sulphuric acid. It should be noted that a combination of
heat exchangers is required to cool the product stream from the converter entering the
intermediate absorption tower and then heat it prior to its return to the converter to meet the
optimum temperature requirements of the converter and the absorbers (Moeller & Winkler,
1968). The primary catalytic converter has a conversion factor of 80 to 93 percent; conversion
efficiency is determined by contact bed patterns and contact time (The European Sulphuric Acid
Association (ESA), 1999). The 99.5 percent conversion is only realized after the intermediate
absorption and subsequent return. The Le Chatelier's principle states that by returning unreacted
SO2 to the column without the result SO3 (after intermediate absorption of SO3), the conversion
reaction's equilibrium becomes more forward biased, converting more SO2.Though this
required an additional couple of heat exchangers and an absorption column, this process results
in an increase in the overall efficiency and hence the productivity. Therein lies our justification
for preference of the DCDA over SCDA as the type of contact process for Sulphuric acid
manufacturing.

2.7 BLOCK FLOW DIAGRAM

Production of Sulphuric acid involves various process units. Having selected the contact process
as the method to be used for the Sulphuric acid production, there are 3 variants of the contact
process, and the Double Contact Double Adsorption (DCDA) process has been selected. In the
double contact process, a primary conversion efficiency of 80% to 93%, depending on the
arrangement of the contact beds and of contact time, is obtained in the primary contact stage of

21
a converter preceding the intermediate absorber (van Nieuwenhuyse). The principle in the
Double Contact Double Absorption system stems from the observation that the unconverted
SO2 of the product stream from the converter could be reduced if the product stream with gases
(SO2) and (SO3) are passed through absorption towers twice to achieve further absorption and
conversion of SO2 to SO3 and thereby production of higher grade Sulfuric acid (Kumareswaran,
2013; MANUFACTURE) .

2.7.1 ESTABLISHING OF PRODUCTION PROCESS

The main steps involved in DCDA process are as below:

1. Melting solid Sulphur with steam coils, followed by filtration or settling of impurities to
obtain clean Sulphur containing less than 10 mg/of ash.

2. Burning the molten Sulphur with air to produce gas containing SO3.

3. Catalytic oxidation of SO2 to SO3 in three consecutive passes of converter containing V2O5
catalyst with intercooling of gas in between. The exothermic heat of reaction is utilized to
produce steam in Waste Heat Boiler system and to reheat the gases going to 4th pass from
the intermediate absorber.

4. Absorption of SO3 (formed in 3rd pass) in the final absorption tower

2.7.2 PROCESS UNITS

Unit One: Sulphur Burning

At a temperature above 1000oC pure Sulphur is melted separately without contact of air for
oxidation into SO2. The molten Sulphur is then fed into a reactor with a counter current flow of
dry air to enhance the oxidation reaction and produce SO2.

Fig 2.3: Sulphur Burning

22
Unit Two: Air Drying

The air supplied to the reactor must be filtered and dried since, if air supply is contaminated
with dust, moisture etc., the poisoning of the catalyst is possible, which can cause a notable
reduction in the conversion efficiency and high utility cost during the operation other than extra
cost of replacement of catalyst.

The finished product (High concentrated H2SO4) can be used in for this purpose theoretically,
however, Oleum is preferred. Partly because using the finished product stream (or pre dilution
Sulfuric stream) again for upstream operations where direct contact will be made with upstream
productsis not appropriate altogether and because Oleum has a higher ability to absorb moisture
due to its more concentrated form. Based on this reason, Oleum will be selected as the
dehydrating medium.

Fig 2.4: Air drying

Unit Three: Gas Cleaning Unit

The Sulphur dioxide produced from combusting molten Sulphur in dry air will contain ash
particles and other which must be removed to ensure the flawless operability of other units such
as the heat exchangers and the converter unit, otherwise could be affected if particulate matter
fouls heat exchangers or in the case of the converter unit- might even affect the catalytic
performance of the catalyst. There is a list of devices that can be used to achieve Gas Cleaning.
The Electrostatic Precipitator has been selected to perform this operation due to its good
efficiency of removing the smallest dust particles with least affect from intense temperatures.
The temperature of the outlet SO2 steam from the filtering unit is around 1000oC. The catalytic
converter that is directly downstream however, needs to be maintained around 450oC to meet
optimum equilibrium conditions. A heat exchanger arrangement may be needed to both cool
this stream and maintain the inlet SO2 stream around 450oC. A heat exchanger is also needed to
cool down the Catalytic converter because the reaction is exothermic.

23
Fig 2.5: Gas cleaning unit

Unit Four: Catalytic Converter

The catalytic converter is the 4-stage packed bed usually in place in the in-contact process. The
reaction in the converter is exothermic reaction where temperature rise is expected. However,
maintaining the 450OC temperature is essential to maintain the maximum conversion around
the optimum equilibrium condition (other than maintaining pressure around the 1-2 atm). The
catalyst plays an important role in the operation of the catalytic converter. The catalyst selected
for this operation is Vanadium (V) Oxide (V2O5) because of its low acquisition cost, low
tendency to contaminate and it is better for large scale production.

Fig 2.6: Catalytic Converter

Unit Five: Intermediate Absorption Tower

24
This unit is inserted in the operation to achieve high conversion efficiency in the conversion of
SO2 to SO3. The produced SO3 is subsequently fed into the main absorption tower. Sulphuric
acid must be fed from storage tanks and the outlet stream of Oleum is sent to their designated
storage tanks.

Fig 2.7: Intermediate Absorption Tower

Unit Six : Main Absorption Tower

SO3 produced reacts with Sulphuric acid (from storage tanks) and produces Oleum. The usual
absorption tower in the contact process is to be selected. The exothermic absorption might
require a heat exchanger to be installed to maintain the temperature of the absorption process to
prevent excessive formation of Sulphuric mist that once formed, will be carried over by in the
flue gas.

25
Fig 2.8: Main Absorption Tower

Unit Seven: Fuel Gas Treatment

Flue gas from the main absorption tower contains oxides of Sulphur and possibly nitrogen too.
A scrubber is required to treat the fuel gas before it is discharged.

Unit Eight: Oleum Tank

The Oleum produced will require a holding tank. The tanks can be used as a starting point for
the distribution of Oleum for the air-drying unit. The Oleum is supplied to the tanks from the
main and intermediate absorption columns.

Unit Nine: Dilution Tank

This is where Oleum is converted to Sulphuric acid. The water flowrate depends on the desired
concentration of Sulphuric acid and the Oleum collection flow rate. These tanks can also be
used to equalize the produced final Sulphuric acid concentration. The Sulphuric acid streams
fed to main and intermediate absorption tower originates from the tank. Tanks should contain

26
agitators to facilitate proper mixing and homogenization. The final product from dilution tanks
should be 98% Sulphuric acid.

Unit Ten: Heat Exchanger

This unit can be installed to capture the heat released during dilution, if necessary.

Fig 2.9: Process flow diagram for production of Sulphuric acid using Double contact process

27
 CHAPTER THREE

3.0 MATERIAL AND ENERGY BALANCE

3.1 Introduction

This chapter presents the summaries of material balance and energy balance of the 10000
litter/day Sulphuric acid production plant obtained from process simulation using Aspen
HYSYS V10.

3.2 Material Balance

Material balances which is the basis of this process design, was taken over the complete process
to determine the quantities of raw materials required and products produced across individual
unit and the entire equipment using the law of mass conservation (Sinnot, 2005). The operating
conditions were obtained from past literature(Davenport et al., 2006), where the following were
imputed into Aspen HYSYS:

At the burner, the Temperature and pressure of 250C and 265kPa were selected to be used
because those were the best conditions and the remaining values needed were generated by the
software.

At the catalytic converters, a constant temperature was maintained at 4500C at the outlet, since
it was an exothermic reaction heat had to be cooled down using a shell and tube heat exchanger.
A multi catalytic bed reactor was selected to be used.

At the 1st catalytic bed, the conversion imputed into Aspen HYSYS was 70%

At the 2nd catalytic bed, the conversion imputed into Aspen HYSYS was 95%

At the 3rd catalytic bed, the conversion imputed into Aspen HYSYS was 98%

At the 4th catalytic bed, the conversion imputed into Aspen HYSYS was 99.9%

For the adsorption column, 10 number of stages were imputed because based on the past
literature it allowed for better contact within the SO3 gas and the H2SO4.

Once three out of five parameters were known i.e. (the temperature, pressure and flowrate), the
remaining values were generated by Aspen HYSYS.

28
Once the values were generated, the scale up factor was calculated using the formula;

𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
Scale up = 𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑏𝑎𝑠𝑖𝑠

Where the production rate: 10,000Ltr/day

All the stream flows were multiplied by the scale up factor gotten.

The mass balances for each component across each unit have been determined for the entire
plant on a daily operations basis. The summary of the Aspen HYSYS simulation result of
material balance across individual equipment units are presented in Table 3.1 to 3.17

3.2.1 MATERIAL BALANCE OF THE PROCESS

Table 3.1: Material Balance Around Burner

Component Input(kg/day) output (kg/day)

sulphur Air product

Oxygen 0.00 5509.88 788.62
SO2 0.00 0.00 9452.26
SO3 0.00 0.00 0.00
H2SO4 0.00 0.00 0.00
Nitrogen 0.00 18145.12 18145.12
H2O 0.00 0.00 0.00
H2S2O7* 0.00 0.00 0.00
Sulphur 4731.00 0.00 0.00
Total 4731.00 23655.00 28386.00

29
Table 3.2: Material Balance Around Heat Exchanger E-100

component Input(kg/day) output(kg/day)

product Water -out steam tube out

Oxygen 788.62 0.00 0.00 788.62
SO2 9452.26 0.00 0.00 9452.26
SO3 0.00 0.00 0.00 0.00
H2SO4 0.00 0.00 0.00 0.00
Nitrogen 18145.12 0.00 0.00 18145.12
H2O 0.00 1443.35 1443.35 0.00
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 28386.00 1443.35 1443.35 28386.00

Table 3.3: Material Balance Around Conversion Reactor C-STAGE 1

component Input(kg/day) output (kg/day)

Tube-out Air2 Stg1-product

Oxygen 788.62 1652.96 1025.14
SO2 9452.26 0.00 3780.90
SO3 0.00 0.00 7087.34
H2SO4 0.00 0.00 0.00
Nitrogen 18145.12 5443.54 23588.65
H2O 0.00 0.00 0.00
H2S2O7* 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00
Total 28386.00 7096.50 35482.04

30
Table 3.4: Material Balance Around Heat Exchanger E-101

component Input(kg/day) output(kg/day)

Stg1-product Water 1 steam 1 Stg-1 out

Oxygen 1025.14 0.00 0.00 1025.14
SO2 3780.90 0.00 0.00 3780.90
SO3 7087.34 0.00 0.00 7087.34
H2SO4 0.00 0.00 0.00 0.00
Nitrogen 23588.65 0.00 0.00 23588.65
H2O 0.00 1623.63 1623.63 0.00
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 35482.04 1623.63 1623.63 35482.04

Table 3.5: Material Balance Around Conversion Reactor C-STAGE 2

component Input(kg/day) output (kg/day)

Stg1- out Stg2-prod

Oxygen 1025.14 354.69

SO2 3780.90 1096.46
SO3 7087.34 10442.02
H2SO4 0.00 0.00
Nitrogen 23588.65 23588.65
H2O 0.00 0.00
H2S2O7* 0.00 0.00
Sulphur 0.00 0.00
Total 35482.04 35481.82

31
Table 3.6: Material balance around heat exchanger E-102

component Input(kg/day) output(kg/day)

Stg2-product Water 2 steam 2 Stg-2
out
Oxygen 354.69 0.00 0.00 354.69
SO2 1096.46 0.00 0.00 1096.46
SO3 10442.02 0.00 0.00 10442.02
H2SO4 0.00 0.00 0.00 0.00
Nitrogen 23588.65 0.00 0.00 23588.65
H2O 0.00 1276.57 1276.57 0.00
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 35481.82 1276.57 1276.57 35481.82

Table 3.7: Material Balance Around Conversion Reactor C-STAGE 3

Component Input (Kg/Day) Output (Kg/Day)

Stg2-Out Stg3-Prod
Oxygen 354.69 146.57
SO2 0.00 0.00
SO3 1096.46 263.15
H2SO4 10442.02 11483.38
Nitrogen 0.00 0.00
H2O 23588.65 23588.65
H2S2O7* 0.00 0.00
Sulphur 0.00 0.00
Total 35481.82 35481.75

32
Table 3.8: Material Balance Around Heat Exchanger E-103

component Input(kg/day) output(kg/day)

Stg3-product Water 3 steam 3 Stg-3 out
Oxygen 146.57 0.00 0.00 146.57
SO2 263.15 0.00 0.00 263.15
SO3 11483.38 0.00 0.00 11483.38
H2SO4 0.00 0.00 0.00 0.00
Nitrogen 23588.65 0.00 0.00 23588.65
H2O 0.00 4874.77 4874.77 0.00
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 35481.75 4874.77 4874.77 35481.75

Table 3.9: Material Balance Around ABSORBER-1

component Input(kg/day) output(kg/day)

Stg3-out H2SO4 gas liquid
Oxygen 146.57 0.00 146.57 0.00
SO2 263.15 0.00 263.14 0.01
SO3 11483.38 0.00 11482.22 1.16
H2SO4 0.00 3852.63 3468.26 384.36
Nitrogen 23588.65 0.00 23588.58 0.08
H2O 0.00 78.63 78.63 0.00
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 35481.75 3931.25 39027.39 385.61

33
Table 3.10: Material Balance Around Conversion Reactor C-STAGE 4

Component Input(kg/day) output (kg/day)

GAS Prod 22
Oxygen 146.57 80.91
SO2 263.14 0.26
SO3 11482.22 11810.73
H2SO4 3468.26 3468.26
Nitrogen 23588.58 23588.58
H2O 78.63 78.63
H2S2O7* 0.00 0.00
Sulphur 0.00 0.00
Total 39027.39 39027.37

Table 3.11: Material Balance Around Heat Exchanger E-104

Component Input(kg/day) output(kg/day)

prod 22 water 4 steam 4 prod 33
Oxygen 80.91 0.00 0.00 80.91
SO2 0.26 0.00 0.00 0.26
SO3 11810.73 0.00 0.00 11810.73
H2SO4 3468.26 0.00 0.00 3468.26
Nitrogen 23588.58 0.00 0.00 23588.58
H2O 78.63 62466.17 62466.17 78.63
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 39027.37 62466.17 62466.17 39027.37

34
Table 3.12: Material Balance Around ABSORBER-2

Component Input(kg/day) output(kg/day)

prod 33 H2O Gas 1 Acid 1
Oxygen 80.91 0.00 80.89 0.02
SO2 0.26 0.00 0.26 0.00
SO3 11810.73 0.00 2.24 0.12
H2SO4 3468.26 0.00 4.05 17930.82
Nitrogen 23588.58 0.00 23582.42 6.16
H2O 78.63 2788.32 208.78 0.97
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 39027.37 2788.32 23878.64 17938.10

Table 3.13: Material Balance Around Mixer MIX-100

Component Input(kg/day) output (kg/day)

Acid 1 Liquid H2SO4-1
Oxygen 0.02 0.00 0.03
SO2 0.00 0.01 0.02
SO3 0.12 1.16 1.28
H2SO4 17930.82 384.36 18315.19
Nitrogen 6.16 0.08 6.23
H2O 0.97 0.00 0.97
H2S2O7* 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00
Total 17938.10 385.61 18323.71

35
Table 3.14: Material Balance Around Heat Exchanger E-105

Component Input(kg/day) output(kg/day)

H2SO4-1 Water5 H2SO42 Water 55

Oxygen 0.03 0.00 0.03 0.00
SO2 0.02 0.00 0.02 0.00
SO3 1.28 0.00 1.28 0.00
H2SO4 18315.19 0.00 18315.19 0.00
Nitrogen 6.23 0.00 6.23 0.00
H2O 0.97 380709.27 0.97 380709.27
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 18323.71 380709.27 18323.71 380709.27

Table 3.15: Material Balance Around Dilution Tank

Component Input(kg/day) output(kg/day)

H2SO4-2 Dilution vent 1 H2SO4
water prod
Oxygen 0.03 0.00 0.00 0.02
SO2 0.02 0.00 0.00 0.02
SO3 1.28 0.00 0.00 1.28
H2SO4 18315.19 0.00 0.00 18315.19
Nitrogen 6.23 0.00 1.18 5.05
H2O 0.97 36.84 0.04 37.77
H2S2O7* 0.00 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00 0.00
Total 18323.71 36.84 1.22 18359.33

36
Table 3.16: Material Balance Around Steam Drum

Component Input(kg/day) Input(kg/day) Output(kg/day)

steam 1 steam 2 steam 3 steam Steam-1 Drain
Oxygen 0 0.00 0.00 0.00 0 0
SO2 0 0.00 0.00 0.00 0 0
SO3 0 0.00 0.00 0.00 0 0
H2SO4 0 0.00 0.00 0.00 0 0
Nitrogen 0 0.00 0.00 0.00 0 0
H2O 1623.631162 1276.57 4874.77 1443.35 3686.139 5532.182
H2S2O7* 0 0.00 0.00 0.00 0 0
Sulphur 0 0.00 0.00 0.00 0 0
Total 1623.63 1276.57 4874.77 1443.35 3686.14 5532.18

Table 3.17: Material Balance Water Storage

Component Input(kg/day) output (kg/day)

WW Vent Water
Oxygen 0.00 0.00 0.00
SO2 0.00 0.00 0.00
SO3 0.00 0.00 0.00
H2SO4 0.00 0.00 0.00

Nitrogen 0.00 0.00 0.00

H2O 71684.49 0.00 71684.49
H2S2O7* 0.00 0.00 0.00
Sulphur 0.00 0.00 0.00
Total 71684.49 0.00 71684.49

37
3.3 Energy Balance

Energy balance was also carried out across individual equipment and the entire process to
determine the heating and cooling requirement of the process due to sensible heat (heat due to
temperature difference). The law of conservation of energy was applied considering the fact
that energy can be generated or consumed in a chemical process. In this regard, the total
enthalpy of outlet streams will not equal that of the inlet streams around the flare or units where
energy is generated (that due to heat of reaction) or consumed. In process design, energy balance
was carried out to determine the energy requirement of the process (heating and cooling duty).
The energy balance of the entire plant is carried out by estimating the enthalpies of all the
streams present in the process using Aspen HYSYS simulation. The heat flow duty was already
generated by the software considering all the parameters imputed. The summary of the Aspen
HYSYS simulation result of energy balance across individual equipment units are presented in
Table 3.18 to 3.37

Table 3.18: Energy Balance Around Burner

Parameter Input (kJ/hr) Output (kJ/hr)

Sulphur Air Product
Heat Flow -473629.13 1427.30 -1162915.24
Duty = -690713.41

Table 3.19: Energy Balance Around Heat Exchanger E-100

Parameter Input (kJ/hr) Output (kJ/hr)

Product Water-out Tube-out steam
Heat Flow -1162915.24 -950197.66 -1356431.76 -756681.13
Duty = 1.02E-08

38
Table 3.20: Energy Balance Around Conversion Reactor C-STAGE 1

Parameter Input (kJ/hr) Output (kJ/hr)

Tube out Air 2 Stage 1 Product
Heat Flow -1356431.76 428.19 -1355995.56
Duty = 8.01

Table 3.21: Energy Balance Around Heat Exchanger E-101

Parameter Input (kJ/hr) Output (kJ/hr)

Stg 1-Product Water 1 Stg-1 out steam 1
Heat Flow -1355995.56 -1068879.92 -1355995.56 -851192.66
Duty = 217687.3

Table 3.22: Energy Balance Around Conversion Reactor C-STAGE 2

Parameter Input (kJ/hr) Output(kJ/hr)

Stg 1 out Stg2 product
Heat Flow -1355995.56 -1573670.4
Duty = 15.02

Table 3.23: Energy Balance Around Heat Exchanger E-102

Parameter Input (kJ/hr) Output (kJ/hr)

stg2 Product Water 2 Stg 2 out steam 2
Heat Flow -1573670.40 -840399.04 -1744825.42 -669244.02
Duty = 1.02E-08

39
Table 3.24: Energy Balance Around Conversion Reactor C-STAGE 3

Parameter Input (kJ/hr) Output(kJ/hr)

Stg 2out Stg3 product
Heat Flow -1744825.42 -1744809.073
Duty = 15.02

Table 3.25: Energy Balance Around Heat Exchanger E-103

Parameter Input (kJ/hr) Output (kJ/hr)

stg3 Product Water 3 Stg 3 out steam 3
Heat Flow -1744809.07 -3209191.49 -1811460.73 -3142539.84
Duty = 1.02E-08

Table 3.26: Energy Balance Around Absorber-1

Parameter Input (kJ/hr) Output (kJ/hr)

Stg 3-out H2SO4 Gas Liquid
Heat Flow -1811460.73 -1589056.02 -3256283.16 -144233.58
Duty = 0.00E+00

Table 3.27: Energy Balance Around Conversion Reactor C-STAGE 4

Parameter Input (kJ/hr) Output(kJ/hr)

Gas Prod22
Heat Flow -3256262.56 -3781677.091
Duty = -525414.53

40
Table 3.28: Energy Balance Around Heat Exchanger E-104

Parameter Input (kJ/hr) Output (kJ/hr)

Prod 22 water 4 Prod 33 steam 4
Heat Flow -3781677.09 -41123155.93 -3771421.28 -40607997.21
Duty = 5.25E+05

Table 3.29: Energy Balance Around Absorber-2

Parameter Input (kJ/hr) Output (kJ/hr)

Prod 33 H2O Acid 1 Gas 1
Heat Flow -3771421.28 -1834877.00 -7016565.10 -39679.33
Duty = -1.45E+06

Table 3.30: Energy Balance Around Mixer MIX-100

Parameter Input (kJ/hr) Output (kJ/hr)

Acid 1 Liquid H2SO4-1
Heat Flow -7016565.10 -144233.58 -7160798.68
Duty = 0.00

Table 3.31: Energy Balance Around Heat Exchanger E-105

Parameter Input (kJ/hr) Output (kJ/hr)

H2SO4-1 Water 5 H2SO4-2 Water 55
Heat Flow -6923490.15 -184888679.60 -7317026.75 -184495143.00
Duty = -5.39E-06

41
Table 3.32: Energy Balance Around Pump P-101

Parameter Input (kJ/hr) Output (kJ/hr)

Water F W3 Water 5
Heat Flow -250731526.70 5280.35 -250726246.35
Duty = 0.00

Table 3.33: Energy Balance Around Dilution Tank

Parameter Input (kJ/hr) Output (kJ/hr)

H2SO4-2 Dilution H2SO4 prod Vent 1
water
Heat Flow -7317026.75 -24263.50 -7331987.25 -22.57
Duty = 9.28E+03

Table 3.34: Energy Balance Around Water Storage

Parameter Input (kJ/hr) Output (kJ/hr)

WW Vent Water
Heat Flow -2920190.50 0.00 -2920190.50
Duty = 0.00

Table 3.35: Energy Balance Around Pump P-100

Parameter Input (kJ/hr) Output (kJ/hr)

Water W DM Water
Heat Flow -47210730.13 18906.09 -47191824.04
Duty = 0.00

42
 Table 3.36: Energy Balance Around TEE-100
Parameter Input (kJ/hr) Input (kJ/hr)

DM Water Water out Water1 Water 2 Water 3 Water 4

Heat Flow -47191824.04 -950197.6555 -1068879.923 -840399.0417 -3209191.49 -41123155.93

Duty = 0.00

Table 3.37: Energy Balance Around Steam Drum

Parameter Input (kJ/hr Output (kJ/hr)

Steam 1 Steam 2 Steam 3 Steam Steam-1 Drain

Heat Flow -851192.66 -669244.02 -3142539.84 -756681.13 -2013263.38 -3406394.27

Duty = 0

43
CHAPTER FIVE

5.0 EQUIPMENT DESIGN AND SPECIFICATIONS

5.1 Introduction

This chapter present the results of the equipment sizing and specification of the various
equipment units present in the sulphuric acid production process as well as the specification for
material of construction.

5.2 Equipment Design

Aspen HYSYS Simulation of the Production Process

The production process for sulphuric acid was simulated using Aspen HYSYS V10. The PFD
of the process was first drafted with required operating condition established from literatures
and components involved in the process. The Aspen HYSYS software was launched, opening
up the Properties Environment where all the components involved in the entire process were
selected (Oxygen, Nitrogen, S_Liq_280 (Sulphur), SO2, SO3, H2SO4 and H2O). The Antoine
Fluid Package (the mathematical algorithm for estimation of the fluid properties) was selected
been the best fluid package in handling sulphuric acid process available in Aspen HYSYS.

Also, the various reactions involved were defined from the Reactions section of the Properties
Environment. Conversion reactions were specified because the reaction information available
from the literature were conversion information.

The reactors and equipment were design on 85% material volume (i.e., 15% allowance of safety
was use during the equipment sizing). The volumetric flowrate obtained from material and
energy balance simulation were automatically used for the equipment sizing.

Reactor

A conversion reactor was selected to be used. The Conversion Reactor is a CSTR with a
specialization in conversion reactions and thus can only function with reaction sets including
that reaction type. The conversion reactor enabled us to input the reaction set of the process with
its stoichiometry and coefficient on Aspen HYSYS

44
Converter

Vanadium pentoxide (V2O5) catalyst is utilized as the SO2 to SO3 converter catalyst considered
for this design. This because it’s a cheaper and successful option for the catalyst converter and
also had the added advantage of being more robust to catalyst poisoning and subsequent
deactivation.

Diameter of 0.797 m was considered because it’s the nearest standard pipe size to the initially
design pipe size (0.791 m).

Inter-stage allowance of 0.55 m was considered to allow for discharge stream from previous
stage and feed to preceding stage after cooling to 450 oC.

Top and bottom stream allowance of 0.7 m was considered to allow for reactor internal such as
inlet distributor, catalyst support and product collector.

Material of Construction

Materials of construction in sulfuric acid manufacturing plants are typically limited to carbon
steel, refractory-lined carbon steel, Type 304 or 304H stainless steel, and Incoloy 800H.

Carbon steel is used in cooler sections of the plant, typically at temperatures below about 900°F.
Carbon steel may be lined with a polymeric coating for corrosion resistance when operating
temperatures are low enough for acid condensation. Refractory-lined or brick-lined carbon steel
is used in the hottest sections of the plant, where temperatures typically exceed 1800°F. Types
304 and 304H stainless steels are used in ducting that operates in the 900°-1200°F temperature
range.

Pumps

The pumps were sized using material and energy balance result while the pump curve were
generated in Aspen HYSYS base on the volumetric flow rate of liquid been pump to determine
the pump speed, efficiency, Pressure head, capacity, Net Positive Suction Head available and
required (NPSHa and NPSHr).

45
Heat Exchanger

The heat exchanger were design and size using the Aspen HYSYS Aspen Exchanger Design
and Rating (EDR) tools. The Shell and Tube Exchanger Design/Rating Analysis is a powerful
tool in Aspen HYSYS for detailed design of heat transfer equipment. It uses the Aspen
Exchanger Design and Rating (EDR) exchanger model to design or rate/check a Shell and Tube
Heat Exchanger.

The results obtained from the material and energy balance was use to automatically size the heat
exchanger using the EDR by directly which then comes up with a suitable sizing result the meets
the operational requirement and capacity base on the material and energy balance result.

The design results obtained from are presented in tables below. Further details of the equipment
design will be presented in the Appendix.

Table 5.1: Design Specifications for Burner

Parameters Design Specification

Item Burner/Furnace
Number Required 1
Identification CRV-100
Function Burn Sulphur to SO2
Heat Transfer Area [m2] 7.707
Diameter [m] 1.279
Total Length [m] 1.918
L/D Ratio 1.499
Design Volume [m3] 2.464
Material Percent Level [%] 50
Material of Construction Carbon Steel, ASTM A387
Orientation Vertical
Head and Dish Type Ellipsoidal head and dish

46
Table 5.2: Design Specifications for Heat Exchanger 1

Specification Parameter Manual Calculation

Item Waste Heat Recovery Exchanger

Number Require 1

Identification E-100

Function Steam generation from burner effluent

waste heat

Material of Construction Stainless Steel Type 304L

Orientation Horizontal

Exchanger Duty (kJ/hr) 53.8

Log Mean Temperature (oC) 127.58

Corrected Log Mean Temperature (oC) 214.12

Heat Transfer Area (m2) 3.2

Baffle Spacing, (mm) 150

Number of Baffle 6

Tube Pitch (mm) 0.0238

Pitch Type Plain

Safe Working Pressure (kPa) 4830

Design Pressure (kPa) 5400

Overall heat transfer coefficient (W/m2K) 310.8

Tube Shell

Fluid Allocation Product/tube out Water-out/steam

47
Passes 1 1

Inlet Temperature (oC) 600 261.78

Outlet Temperature (oC) 440.17 512.53

Flow Rate (kg/hr) 1183 83

Internal Diameter (mm) 13.51 200

Outer Diameter (mm) 19.05 284

Number 49 1

Length (m) 1.2 1.2

Average Temperature (oC) 635 535

Linear Velocity (m/sec) 37 0.23

Heat Transfer Coefficient (W/m2K) 118.9 310.8

Fouling Coefficient (W/m-2K) 1576.3 2272.7

Pressure Drop (kPa) 3.096 0.532

Table 5.3: Design Specifications for Heat Exchanger 2

Specification Parameter Manual Calculation

Item Waste Heat Recovery Exchanger

Number Require 1

Identification E-101

Function Steam generation from converter 1

48
Material of Construction Stainless Steel Type 304L

Orientation Horizontal

Exchanger Duty (kJ/hr) 63.5

Log Mean Temperature (oC) 130.62

Corrected Log Mean Temperature (oC) 214.3

Heat Transfer Area (m2) 3.2

Baffle Spacing, (mm) 150

Number of Baffle 6

Tube Pitch (mm) 23.81

Pitch Type plain

Safe Working Pressure (kPa) 4830

Design Pressure (kPa) 5400

Overall heat transfer coefficient (W/m2K) 353.4

Tube Shell

Fluid Allocation Stg 1 prod/Stg 2-out Water 1/Steam 1

Passes 1 1

Inlet Temperature (oC) 589.32 261.78

Outlet Temperature (oC) 442.89 489.8

Flow Rate (kg/hr) 1478 99

Internal Diameter (mm) 13.51 200

Outer Diameter (mm) 19.05 284

Number 49 1

49
 Length (m) 1.2 1.2

Average Temperature (oC) 625 585

Linear Velocity (m/sec) 46.07 0.27

Heat Transfer Coefficient (W/m2K) 145.1 353,4

Fouling Coefficient (W/m-2K) 1576.3 2222.2

Pressure Drop (kPa) 4.435 0.748

Table 5.4: Design Specifications for Heat Exchanger 3

Specification Parameter Manual Calculation

Item Waste Heat Recovery Exchanger

Number Require 1

Identification E-102

Function Steam generation from Converter 2

Material of Construction Stainless Steel Type 304L

Orientation Horizontal

Exchanger Duty (kJ/hr) 48.4

Log Mean Temperature (oC) 68.82

Corrected Log Mean Temperature (oC) 157.96

Heat Transfer Area (m2) 5.2

Baffle Spacing, (mm) 135

Number of Baffle 6

50
Tube Pitch (mm) 23.81

Pitch Type Plain

Safe Working Pressure (kPa) 4830

Design Pressure (kPa) 5400

Overall heat transfer coefficient (W/m2K) 160.5

Tube Shell

Fluid Allocation stg2 product->Stg2 water 2->steam 2

out

Passes 1 1

Inlet Temperature (oC) 552.19 261.78

Outlet Temperature (oC) 440.89 535.25

Flow Rate (kg/hr) 1478 73

Internal Diameter (mm) 12.24 250

Outer Diameter (mm) 19.05 354

Number 81 1

Length (m) 1.2 1.2

Average Temperature (oC) 590 585

Linear Velocity (m/sec) 32.37 0.15

Heat Transfer Coefficient (W/m2K) 105.1 160.5

Fouling Coefficient (W/m-2K) 1428.1 2222.2

Pressure Drop (kPa) 2.886 0.388

51
Table 5.5: Design Specifications for Heat Exchanger 4

Specification Parameter Manual Calculation

Item Waste Heat Recovery Exchanger

Number Require 1

Identification E-103

Function Steam generation from converter 3

Material of Construction Stainless Steel Type 304L

Orientation Horizontal

Exchanger Duty (kJ/hr) 14.6

Log Mean Temperature (oC) 31.73

Corrected Log Mean Temperature (oC) 103.12

Heat Transfer Area (m2) 3.9

Baffle Spacing, (mm) 145

Number of Baffle 6

Tube Pitch (mm) 23.81

Pitch Type Plain

Safe Working Pressure (kPa) 4830

Design Pressure (kPa) 5400

Overall heat transfer coefficient (W/m2K) 78.8

Tube Shell

Fluid Allocation Stg3 product/ stg Out Water3/Steam3

Passes 1 1

52
 Inlet Temperature (oC) 475.03 261.78

Outlet Temperature (oC) 441.33 474.2

Flow Rate (kg/hr) 1478 23

Internal Diameter (mm) 0.0096 0.225

Outer Diameter (mm) 0.0191 307

Number 60 1

Length (m) 1.2 1.2

Average Temperature (oC) 580 550

Linear Velocity (m/sec) 32.68 0.05

Heat Transfer Coefficient (W/m2K) 121.8 78.8

Fouling Coefficient (W/m-2K) 1542 2173.9

Pressure Drop (kPa) 3.097 1.004

Table 5.6: Design Specifications for Heat Exchanger 5

Specification Parameter Manual Calculation

Item Waste Heat Recovery Exchanger

Number Require 1

Identification E-104

Function Steam generation from Absorber-1

Material of Construction Stainless Steel Type 304L

Orientation Horizontal

53
Exchanger Duty (kJ/hr) 172.2

Log Mean Temperature (oC) 184.09

Corrected Log Mean Temperature (oC) 161.9992

Heat Transfer Area (m2) 6.4

Baffle Spacing, (mm) 190

Number of Baffle 10

Tube Pitch (mm) 0.0238

Pitch Type Plain

Safe Working Pressure (kPa) 1000

Design Pressure (kPa) 1100

Overall heat transfer coefficient (W/m2K) 1976.7

Tube Shell

Fluid Allocation Prod 22/ Prod-33 Water 4/Steam 4

Passes 2 1

Inlet Temperature (oC) 475.03 27.47

Outlet Temperature (oC) 95.53 85.81

Flow Rate (kg/hr) 1626 2523

Internal Diameter (mm) 14.83 205

Outer Diameter (mm) 19.05 219.08

Number 46 1

Length (m) 2.4 2.4

Average Temperature (oC) 82.12 54.39

54
 Linear Velocity (m/sec) 77.81 0.06

Heat Transfer Coefficient (W/m2K) 231.2 1976.7

Fouling Coefficient (W/m-2K) 1557.3 2000

Pressure Drop (kPa) 26.984 1.156

Table 5.7: Design Specifications for Heat Exchanger 6

Specification Parameter Manual Calculation

Item Waste Heat Recovery Exchanger

Number Required 1

Identification E-105

Function Steam generation from converter 4

Material of Construction Stainless Steel Type 304L

Orientation Horizontal

Exchanger Duty (kJ/hr) 14.1

Log Mean Temperature (oC) 22.91

Corrected Log Mean Temperature (oC) 22.46

Heat Transfer Area (m2) 6.4

Baffle Spacing, (mm) 190

Number of Baffle 10

Tube Pitch (mm) 23.81

Pitch Type plain

55
Safe Working Pressure (kPa) 350

Design Pressure (kPa) 400

Overall heat transfer coefficient (W/m2K) 4945.9

Tube Shell

Fluid Allocation H2SO4-1/H2S04-2 Water 5/Water-55

Passes 2 1

Inlet Temperature (oC) 102.7 27.47

Outlet Temperature (oC) 30.8 28.24

Flow Rate (kg/hr) 763 15863

Internal Diameter (mm) 14.83 205

Outer Diameter (mm) 19.05 219.08

Number 46 1

Length (m) 2.4 2.4

Average Temperature (oC) 29.39 27.78

Linear Velocity (m/sec) 25.95 0.38

Heat Transfer Coefficient (W/m2K) 113.9 4945.9

Fouling Coefficient (W/m-2K) 1557.3 2000

Pressure Drop (kPa) 6.348 44.094

56
Table 5.8: Design Specifications for Pump 1

Parameter Design Specification

Item Pump
No. Required 2
Identification P-100 A/B
Function Water pump
Suction Pressure [kPa] 101.3250
Discharge Pressure [kPa] 4821.4308
Volumetric Flowrate [m3/hr] 0.1850
Pressure Head [m] 483.2
NPSH required [m] 0.1484
NPSH available [m] 10.21
Speed [rpm] 3500
Power [kW] 0.3844
Efficiency [%] 63.26
Material of Construction Carbon Steel

Table 5.9: Design Specifications for Pump 2

Parameter Design Specification

Item Pump
No. Required 2
Identification P-101 A/B
Function Water pump
Suction Pressure [kPa] 101.3250
Discharge Pressure [kPa] 350.0000
Volumetric Flowrate [m3/hr] 15.9290
Pressure Head [m] 25.46
NPSH required [m] 5.470

57
 NPSH available [m] 10.27
Speed [rpm] 1150
Power [kW] 1.633
Efficiency [%] 67.51
Material of Construction Carbon Steel

Table 5.10: Design Specifications for Steam Drum

Parameter Design Specification

Item Steam drum
No. Required 1
Identification D-100
Function Steam storage
Diameter [m] 0.9239
Total Length [m] 1.386
L/D Ratio 1.5
Design Volume [m3] 0.9290
Material Percent Level [%] 50.00
Material of Construction Carbon Steel
Orientation Vertical
Head and Dish Type Ellipsoidal head and dish

Table 5.11: Design Specifications for converter

Converter Design Specification

Number Required 1.000

Item Multiple Bed Catalytic Reactor

58
Function Conversion of SO2 to SO3

Catalyst Type Vanadium Pentoxide (V2O5)

Material of Construction Carbon Steel

Orientation Vertical

Stage Feed Temperature 450.000oC

V2O5 Catalyst Density 3357.000kg/m3

Gas Hourly Space Velocity 3443.000/hr (Residence time of 0.869 sec)

Bed Void Fraction 0.450

1st Stage Bed

Tube Out 573.700m3/hr

Air2 96.520m3/hr

Volumetric Rate 670.220m3/hr

Bed volume (Volumetric Rate/GHSV) 0.195m3

H to Diameter ratio (H/D) 0.500

pi 3.142

Reactor Bed Diameter 0.791m

1st Bed height 0.396m

A Uniform Catalyst Bed Diameter (D) 0.797m

New Bed Height (H) 0.390m

New H/D Ratio 0.493

Catalyst Weight 359.414kg

59
2nd Stage Bed

Stg 1 Out 566.900m3/hr

Volumetric Rate 566.900m3/hr

Bed volume (Volumetric Rate/GHSV) 0.165m3

Bed Diameter (Maintaining Uniform 0.797m

reactor diameter)

2nd Bed height 0.330m

New H/D Ratio 0.414

Catalyst Weight 304.007kg

3rd Stage Bed

Stg 2 Out 556.500 m3/hr

Volumetric Rate 556.500 m3/hr

Bed volume (Volumetric Rate/GHSV) 0.162m3

Bed Diameter (Maintaining Uniform 0.797m

reactor diameter)

3rd Bed height 0.324m

New H/D Ratio 0.406

Catalyst Weight 298.430kg

4th Stage Bed

Gas 690.500 m3/hr

60
 Volumetric Rate 690.500 m3/hr

Bed volume (Volumetric Rate/GHSV) 0.201m3

Bed Diameter (Maintaining Uniform 0.797m

reactor diameter)

4th Bed height 0.402m

New H/D Ratio 0.504

Catalyst Weight 370.289kg

Total Bed Volume 0.721m3

Total Catalyst Weight 1332.139kg

Inter-Stage Allowance for Feed and exit 0.550m

stream

Top and bottom Stream Allowance 0.700m

Total Height of 4 Stage Bed Converter 3.796m

Material of Construction Stainless Steel type 304L

Head and Dish Type Ellipsoidal head and dish

Table 5.12: Design Specifications for Absorber 1

Parameter Design Specification

Item Absorber
No. Required 1
Identification C-100
Function Absorption of SO3 by H2SO4 to form Oleum

61
Type Packed Column
Packings Type CMR Packing
Packings Material Ceramics
Packings Dimension NO-2
Packings Vendor Glitsch
Section Starting Stage 1
Number of Stages 10
Section Ending Stage 10
Column Diameter [m] 0.3
Packed Height Per Stage [m] 3.2
Section Height [m] 3.2
Maximum % Capacity (Constant 62.4558
L/V) [%]
Maximum Capacity Factor [m/s] 0.122
Section Pressure Drop [mbar] 17.98
Average Pressure Drop / Height 5.619
[mbar/m]
Average Pressure Drop / Height 5.422
(Frictional) [mbar/m]
Maximum Stage Liquid Holdup [m3] 0.0005313
Maximum Liquid Superficial 1.777
Velocity [m3/h-m2]
Surface area [m2/m3] 98
Void Fraction 0.73
Material of Construction Carbon Steel
Orientation Vertical
Head and Dish Type Ellipsoidal head and dish

62
Table 5.13: Design Specifications for Absorber 2

Parameter Design Specification

Item Absorber
No. Required 1
Identification Absorber-22
Function Absorption of SO3 by H2SO4 to form Oleum
Type Packed Column
Packing Type CMR Packing
Packing Material Ceramics
Packing Dimension NO-2
Packing Vendor Glitsch
Section Starting Stage 1_Main Tower
Number of Stages 10
Section Ending Stage 10_Main Tower
Column Diameter [m] 0.34
Packed Height Per Stage [m] 0.318
Section Height [m] 3.18
Maximum % Capacity (Constant 43.62
L/V) [%]
Maximum Capacity Factor [m/s] 0.08036
Section Pressure Drop [mbar] 7.598
Average Pressure Drop / Height 2.389
[mbar/m]
Average Pressure Drop / Height 2.19
(Frictional) [mbar/m]
Maximum Stage Liquid Holdup [m3] 0.0001714
Maximum Liquid Superficial 0.4667
Velocity [m3/h-m2]
Surface area [m2/m3] 98
Void Fraction 0.73

63
 Material of Construction Carbon Steel
Orientation Vertical
Head and Dish Type Ellipsoidal head and dish

Table 5.14: Design Specifications for water storage

Parameter Design Specification

Item Water storage
No. Required 1
Identification Water storage tank
Function Water storage
Diameter [m] 0.5743
Total Length [m] 0.8614
L/D Ratio 1.499
Design Volume [m3] 0.2314
Material Percent Level [%] 80.00
Material of Construction Carbon Steel
Orientation Vertical
Head and Dish Type Ellipsoidal head and dish

Table 5.15: Design Specifications for Dilution tank

Parameter Design Specification

Item Water storage
No. Required 1
Identification D-100
Function Water dilution
Diameter [m] 0.7610

64
Total Length [m] 1.141
L/D Ratio 1.499
Design Volume [m3] 0.5191
Material Percent Level [%] 80.00
Material of Construction Carbon Steel
Orientation Vertical
Head and Dish Type Ellipsoidal head and dish

65
REFERENCES

1. Davenport, W. G., King, M. J., Rogers, B., & Weissenberger, A. (2006). Sulphuric acid
manufacture. Southern African Pyrometallurgy, 1(1-16).
2. Kumareswaran, S. (2013). Design of a Plant to Manufacture Sulfuric Acid from Sulfur
University of Moratuwa].
3. MANUFACTURE, D. O. A. P. T. CH 4202 COMPREHENSIVE DESIGN PROJECT
GROUP REPORT DESIGN OF A PLANT TO MANUFACTURE SULFURIC ACID
FROM SULFUR.
4. van Nieuwenhuyse, A. E. PRODUCTION OF SULPHURIC ACID.

66