Production of Sulfuric Acid
Production of Sulfuric Acid
Production of Sulfuric Acid
1.1 INTRODUCTION
Sulphuric acid is one of the most important chemical compounds with the
molecular formula H2SO4. It is a clear, colourless, viscous liquid that is very
corrosive. It is soluble in water at all concentrations sulphuric acid is commonly
used in the laboratory. It has many applications, and is one of the top products
of the chemical industry.
Pure sulphuric acid does not exist naturally on earth due to its strong affinity to
water vapor, because of this, it is hygroscopic and readily absorbs water vapor
from the air. Concentrated sulphuric acid is highly corrosive towards other
materials, from rocks to metals since it is an oxidant with powerful dehydrating
properties. Phosphorus pentoxide is a notable since it is not dehydrated by
sulphuric acid, but rather dehydrates sulphuric acid to sulphur trioxide (SO 3). If
sulphuric acid is added to water, a considerable amount of heat is released;
therefore it is not advisable to add water to the acid as the heat released may
boil the solution, spraying droplets of hot acid during the process. When this
acid gets in contact with body tissue it can cause a severe acidic chemical burns
and even secondary thermal (heat) burns due to dehydrating.
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and in various cleaning agents. Sulphuric acid can be obtained by dissolving
sulphur trioxide in water.
There are two properties of sulphuric acid which are the physical and chemical
properties.
Physical properties
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1.1.2 General Properties of Sulphuric Acid
1.2 HISTORY
Sulphuric acid was first called oil of vitriol when Islamic alchemist, astronomer,
and physicist Jabrin Ibn Hayyan (721-815 BC) discovered it in the eight
century. European alchemist also called it oil of vitriol; some called it spirit of
vitriol or vitriol. It was a very popular chemical to alchemist across Asia and
Europe during the eight century to the sixteen century and in later centuries by
chemists. In the seventeen century, German-Dutch alchemist and chemist
Johann Gauber (1604-1670) combined sulphur with salt peter (Potassium
nitrate) and heated the combination with steam to make sulphuric acid.
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Around 1735, sulphuric acid was first mass produced by English pharmacist
Joshua Ward in glass containers. Then, about 15years after, English inventor
John Roebuck (1718-1794) used a lead chamber process that made its
production more efficient and less costly. The process was further improved
over the next eighty years. In 1831, English Merchant Peregrine Philips
designed the contact-process for producing sulphuric acid. His patented process
is now the standard way of producing sulphuric acid in the 2000s.
1.3 OVERVIEW
Sulphuric acid is one of the H2SO4 most important compounds made by the
chemical industry. It is used to made, literally, hundreds of compounds needed
by almost every industry.
Sulphuric acid has many uses, aside from using it in the production of
phosphate fertilizers, calcium dihydrogenphosphate and ammonium phosphate,
it can also be used to make ammonium sulphate which is an important fertilizer
in sulphur-deficient. A pie chart of the uses of sulphuric acid. The largest use is
in the production of phosphate fertilizers
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CHAPTER TWO
1. Extraction of sulphur
2. Conversion of sulphur to sulphur dioxide
3. Conversion of sulphur dioxide to sulphur trioxide
4. Conversion of sulphur trioxide to sulphuric acid
Easily the most important source of sulphur is its recovery from natural gas and
oil. These contain sulphur compounds, both organic and hydrogen sulfide both
of which must be removed before they are used as fuels or chemical feedstock.
Another important source of sulphur is as sulphur dioxide from metal refining.
Many metal ores occur as sulfides and are roasted to form an oxide and sulphur
dioxide, for example, in the manufacture of lead. Other metals manufactured
from their sulfide ores include copper, nickel and zinc.
Worldwide about 35% of the sulphur is obtained as sulphur dioxide from sulfide
ore roasting and this is increasing, as plants which traditionally passed the
sulphur dioxide to atmosphere are recovering it as sulphuric acid. In particular,
China makes most of its sulphuric acid from pyrites, an iron sulfide ore.
Sulphuric acid is also obtained from ammonium sulfate, a by-product in the
manufacture of poly (methyl 2-methylpropenoate) and also recovered from
'spent' (i.e. used) sulphuric acid.
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The sulphur burns with a characteristic blue flame. As excess air is used the
emerging gas contains about 10-12% sulphur dioxide and 10% oxygen, by
volume. The gases are very hot and so are passed through heat exchangers
(waste heat boilers). The gases are cooled to about 700 K and the water in the
surrounding boiler pipes is converted into steam. In manufacturing one tonne of
sulphuric acid, one tonne of high pressure steam is also produced.
A typical plant contains one cylindrical vessel which acts as a fixed bed reactor
with four separate beds of catalyst, known as a converter, heated to 700 K,
through which the sulphur dioxide and air pass. The catalyst, vanadium (V)
oxide on silica, is generally in the form of small pellets, to which caesium
sulfate has been added as a promoter. The function of the promoter is to lower
the melting point of vanadium (V) oxide so that it is molten at 700 K.
The reaction of sulphur dioxide and oxygen is exothermic so, for a satisfactory
yield of sulphur trioxide, as low a temperature as economically possible is used.
Thus, heat is removed from the gas leaving each of the four beds using heat
exchangers. The sulphur trioxide produced is removed between the third and
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fourth beds and flows to the next stage, the conversion of sulphur trioxide to
sulphuric acid
The sulphur trioxide formed from the third bed (and the small amount from the
fourth bed) are now converted to sulphuric acid. However, water itself cannot
be used for absorption as there is a large temperature rise, and a sulphuric acid
mist is formed, which is difficult to handle. Instead, sulphuric acid of about
98% concentration is used. This is kept at this concentration by addition of
water and removal of acid at that concentration. To keep the temperature at
about 400 K, the heat is removed by heat exchangers.
The gases not absorbed contain about 95% nitrogen, 5% oxygen, and traces of
sulphur dioxide. The gas stream is filtered to remove any traces of sulphuric
acid mist and is returned to the atmosphere using a high stack.
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2.2 PRODUCTION TECHNIQUES FOR THE PRODUCTION OF
SULPHURIC ACID
There are basically two major techniques that are involved in the manufacturing
of sulphuric acid;
The lead chamber is used to produce much of the acid used to make fertilizers;
it produces a relatively dilute acid 62 %−78 % H 2SO4 . A typical flow diagram for
the chamber process is represented in fig.1. The chamber process starts when
sulphur or pyrite is burned and the hot gases are conducted through a
combustion chamber which also may collect some dust. Sufficient oxides of
nitrogen NO and NO2 are introduced into the hot mixture of air and sulphur
dioxide. This may be done either by the use of niter pots or by an
ammonia oxidation unit.
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The hot gaseous mixture passes up the Glover tower where it is met by the
downward flow of the diluted Gay-Lussac acid or the nitrous vitriol. In the
glover tower about 10% of the sulphuric acid is produced, also called tower
acid. If an ammonia oxidation unit supplies the nitrogen oxide, this is preferably
entered into the gaseous stream, after the gas has been cooled by passing it
through the Glover tower. The cooled gases are blown to the chambers where
most of the acids is made and condensed. Finally, the un-reacted gases pass to
the Gay tower for the absorption of the oxides of nitrogen in the strong Glover
acid, producing the Gay-Lussac acid or the nitrous vitriol. The conversion of the
sulphur dioxide to sulphuric acid involves many complex chemical changes.
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( S O2 )(g) + 2 O2(g )+ H 2 O(l ) → H 2 S O4(l)
Until 1900 no contact process plant had built in the United States, although this
process had become very important in Europe because of their need for oleums
and high-strength acid for sulfonation, particularly in the dye industry.
In contact process, purified sulphur dioxide and air are mixed, heated to about
450°c and passed over a catalyst; the sulphur dioxide is oxidized to form
sulphur trioxide. The catalyst is usually platinum on a silica or asbestos carrier
or vanadium pentoxide on a silica carrier. The sulphur trioxide is cooled and
passed through two towers.
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In the first tower it is washed with oleum (fuming sulphuric acid 100%
sulphuric acid with sulphur trioxide dissolved in it). In the second tower it is
washed with 97%sulphuric acid, 98% sulphuric acid is usually produced in this
tower. Waste gases are usually discharged into the atmosphere, acid of any
desired concentration may be produced by mixing or diluting the product of this
process.
The diagram above shows the production processes of sulphuric acid by the
contact process.
O2 oleumH2O
(Excess air)
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CHAPTER THREE
Just like industries that manufactures goods, food companies and their
associations commonly promotes “good manufacturing practices” (GMP) as a
key measure to help ensure consistent acceptable product quality and safety. An
effective GMP reduces risk, helps companies save money, upholds a company’s
reputation and helps to create a competitive edge in an increasingly crowded
market place , one f the most critical components of GMP is quality control
(QC) , the process of sampling, testing and comparing results with pre-agreed
specification as part of the overall quality assurance process.
1. People
2. Premises
3. Processes
4. Products
5. Procedures (or paper work)
Acid factories should respect proper sanitation, regular cleaning habits and
personal hygiene measures to prevent and control hazards.
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Sulphuric acids or products that contain concentrated Sulphuric acid should be
stored in a cool, dry area away from sunlight and heat sources. Sulphuric acids
should not be stored indoors in large quantities to prevent the possible
accumulation of vapours. Poor containers should be regularly examined by
professional MSDS experts for signs of damage or leaks. Proper Sulphuric acid
safety is extremely important. When handling Sulphuric acid in a laboratory or
industrial setting, or when using products that contains concentrated Sulphuric
acid, its important to prioritize safety procedures. The following protective
equipment should be worn when using Sulphuric acid:
1. Respirator
2. Long Rubber Gloves
3. Boots
4. Industrial Apron
5. Chemical Safety Google
6. Face Shield.
This is to ensure that the Sulphur levels are the adequate required measurement
during its manufacturing and storage before it leaves a factory. This is among
the duties of the quality manager.
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CHAPTER FOUR
OPERATION PROBLEMS
Thus, there are difficulties that are encountered in the plant as in its construction
process. Corrosion and construction problems and the most problems that are
involved in the process of constructing and producing sulphuric acid (H 2SO4).
Moreover, there are other areas that sulphuric acid production process has
causes great problems and that must be looked into.
Reduction of emission
Raw materials
Energy recovery
Recycling of spent acids and by products.
1. Reduction of emissions: The emission of SO2 could be reduced
substantially by introduction of the double contact process developed by the
BAYER AG. The principle of the process is described.
2. Raw materials: There is a world-wide tendency towards the use of
elementary sulphur. The resulting technical consequences are discussed
3. Energy recovery: During the manufacture of sulphuric acid large quantities
of heat are produced. Regarding the present energy, the recovery of this
energy is an important necessity. The heat from the formation of SO 2 to SO3
is recovered to a large extent and is converted to high pressure steam.
Presently, large efforts are made in order to use the heat from the reaction
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with water. A number of technical possibilities together with some materials
problems are discussed.
4. Recycling of spent acids and by-products: the reuse or recycling of spent
acid plays an increasing role. The technical solutions and possible are
possible for the recovery of spent acids with organic as well as inorganic
load by concentration and cleavage processes.
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CHAPTER 5
Consumption
End Use %
Phosphoric acid and fertilizer 70
production 5
Copper leaching 4
Petroleum alkylation 3
Pulp and paper 2
Ammonium Sulphate 1
Aluminium Sulphate 15
Other
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In a larger sense, sulphuric acid is used in the making of almost all
manufactured goods and has a wide range of other applications. The
manufacturing of fertilizers, such as superphosphate of lime and ammonium
sulphate, is the primary usage of sulphuric acid. In the production of synthetic
detergents, dyes and pigments, explosives, medicines, and hydrochloric and
nitric acids, for example, it is also commonly utilized. Sulphuric acid also finds
usage in the refinement of petroleum, where it is used to remove contaminants
from gasoline and other refinery products. A growing part of consumption is
consumed by the metal sector, for example, while washing iron and steel before
coating it with tin or zinc. Sulphuric acid, sometimes known as "battery acid,"
which contains roughly 33% H2SO4, is used to make rayon, which serves as the
electrolyte in lead-acid storage batteries that are frequently used in automobiles.
Market
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elemental sulphur are frequently obtained through petroleum refining by-
products.
Sulphuric acid is one of the world’s largest volume industries, and arguably the
largest industrial chemical produced by mass in the United States. According to
news articles and market projections provided by industrial experts, and
industry specific data providers, demand for Sulphuric acid for the next few
years seem to be growing at a rate of 1.5-2.5%. When analyzing the nature of
the demand for Sulphuric acid, several attributes were observed. In general
however, it is worthwhile mentioning that the multifarious industrial
applications of Sulphuric acid, that spans across many facets of the
manufacturing industry, catering to a wide range of human needs is the driving
force behind this trend in demand. For instance, fertilizer demand for Sulphuric
acid is forecast to grow at about 2.3% during 2015–2029. In response, several
new phosphate fertilizer plants are scheduled to be constructed over the forecast
period, mostly in northern Africa, the Middle East and China. Industrial
observers’ further point out that non fertilizer Sulphuric acid demand will come
primarily from nickel and other metal processing operations. Being a
downstream industry of Sulphuric acid, this has profound implications on the
overall market for Sulphuric acid.
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Figure 5.1; Market volume of sulphuric acid worldwide from 2015 to 2021,
with a forecast for 2022 to 2029 (in million metric tons)
5.2 Cost
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S (l) + O2 (g) → SO2 (g)
1, 000 kmol
= 2× day
=2 ,000 kmol /day
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Steam (300 tons) = $5460
The chemical engineering plant cost index (CEPCI) takes into account most
factors that may have affected a plant cost between 1989 and the present. Since
this index is specifically defined for plant costing and comparison with previous
years, the reliability of above is likely to be high. The CEPCI for 1989 was
approximated as 350.0 while 2022 index was obtained as 585.7 (Chemical
Engineering Plant Cost Index (averaged over year))
Variable cost
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Fixed Cost
Total = $2248341
Total investment
Payback Period = Direct production cost
$ 8000000
= $ 2248341
= 3.56 years
$ 2248341
= $ 8000000 ×100
= 28.10%
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CHAPTER SIX
Sulphur dioxide (SO2) in high concentrations can affect breathing and may
aggravate existing respiratory and cardiovascular disease. It is also a corrosive
chemical and can severely burn the skin and eyes. It may case third degree
burns and blindness on contact. Exposure to sulphuric acid mist can irritate the
eyes, nose, throat and lungs and at higher levels can cause a buildup of fluid in
the lungs. It can also cause permanent damage to the lungs and teeth and can
burn holes in the stomach if swallowed.
Sulphuric acid is very corrosive and would badly burn any plants, birds or land
animals exposed to it. It has moderate chronic long-term toxicity to aquatic life.
Industrial emission of sulphuric acid can produce elevated concentrations in the
atmosphere as it will exist as particles or droplet which may dissolve in cloud,
fog, rain, dew or snow, resulting in very dilute acid solution.
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REFERENCES
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