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1.0 Introduction
Sulphuric acid (H2SO4) is one of the most important compounds made by the chemical
industry. It is used to make, literally, hundreds of compounds needed by almost every
industry. There are two major processes in production of sulphuric acid, they are by contact
process and lead chambers and it is available commercially in a number of grades and
concentration. The contact process produces a purer, more concentrated acid but require purer
raw materials and the use of expensive catalyst. The lead chamber process is used to produce
much of the acid used to make fertilizers. It produces a relatively dilute acid (62% - 78%
H2SO4). In both processes Sulphur dioxide is oxidized and dissolved in water. Some
sulphuric acid is also made from ferrous sulphate waste solutions from pickling iron and steel
and from waste acid sludge from oil refineries.
They are many uses of Sulphuric Acid (H2SO4) in industries. By far the largest amount
of sulfuric acid is used to make phosphoric acid to make the phosphate fertilizers, calcium
dihydrogenphosphate and the ammonium phosphates. It is also used to make ammonium
sulfate, which is a particularly important fertilizer in sulfur-deficient.
fibres
6%
metal processing
13%
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Figure 1 showed the percentage of uses if sulphuric acid in industries. 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. It is also used to make caprolactam, which is
converted into polyamide 6 and in the manufacture of titanium dioxide, used, for example, as
a pigment.Amongst its many other uses is in the manufacture of hydrofluoric acid and phenol
with propanone all of which are used in many industries.
a) Extraction of Sulphur.
b) Conversion of Sulphur to sulphur dioxide.
c) Conversion of sulphur dioxide to sulphur trioxide.
d) Conversion of sulphur trioxide to sulphuric acid.
Easily the most important source of sulfur is its recovery from natural gas and
oil. These contain sulfur 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
sulfur is as sulfur dioxide from metal refining. Many metal ores occur as sulfides and are
roasted to form an oxide and sulfur 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 sulfur is obtained as sulfur dioxide from sulfide ore roasting and
this is increasing, as plants which traditionally passed the sulfur dioxide to atmosphere are
recovering it as sulfuric acid. In particular, China makes most of its sulfuric acid from pyrites,
an iron sulfide ore. Sulfuric acid is also obtained from ammonium sulfate, a by-product in the
manufacture of poly (methyl 2-methylpropenoate) and also recovered from 'spent' sulfuric
acid.
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If sulfur is the feedstock, it must first be converted to sulfur dioxide. Molten sulfur is
sprayed into a furnace and burnt in a blast of dry air at about 1300 K. The sulfur burns with a
characteristic blue flame:
As excess air is used the emerging gas contains about 10-12% sulfur 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 sulfuric 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
sulfur 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 (Figure 2). The function of the promoter
is to lower the melting point of vanadium(V) oxide so that it is molten at 700 K.
The sulfur trioxide formed from the third bed (and the small amount from the fourth
bed) are now converted tosulfuric acid. Sulfur trioxide reacts with water and the reaction can
be expressed as:
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However, water itself cannot be used for absorption as there is a large temperature rise,
and a sulfuric acid mist is formed, which is difficult to handle. Instead, sulfuric 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, Figure 2.
Figure 2: A line diagram illustrating a heat exchanger used in the manufacture of sulfur
trioxide.
The gases not absorbed contain about 95% nitrogen, 5% oxygen, and traces of sulfur
dioxide. The gas stream is filtered to remove any traces of sulfuric acid mist and is returned
to the atmosphere using a high stack.
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Industry has entered into a new age. This can be seen in the advancements of
instrumentations that have brought a very important changes in industry. For example, today,
most products are manufactured using some type of automatically controlled processing
equipment. This equipment is often complex, demanding a variety of skilled personnel to
keep it in operation. At one time, most industrial equipment could be easily placed into
operation with just a few simple tools and some basic common sense. Today the situation
differs in that a large part of equipment and processes contain numerous control devices vital
to the performance of precise automatic operations.The instrumentation calibration techniques
and troubleshooting methods is needed in order to keep things in a good state of repair and
reliability.
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2.1 PFD
PFD is depicting a given systems flows, temperature, pressure and mass balance for
various operating conditions. Such information is typically presented in the form of tables.
PFD present functional information about a system or subsystem. The components such as
piping, pumps and valves are represented by standard schematic symbols that illustrate their
function in the system, as opposed to their relative sizes, locations or physical shapes. The
instrumentation and control information is not included. PFD are typically the first drawing
developed by mechanical processes, often in the pre-conceptual or conceptual design place.
2.2 P&ID
P&ID are typically developed from PFD. P&ID communicated detailed information
on how to operate, troubleshoot and repair or modify the system or subsystem . In addition to
the mechanical components, they include instruments, signal modifiers, controllers and their
inter-relationship. They typically do not include tabular parameters as PFD do. P&ID is a very
common term used in the world of process industries. A process engineer in a manufacturing
plant need to create new and/or modify the already existing P&ID to the as-is plant
modifications. A P&ID is a detailed graphical representation of a process including the
hardware and software (piping, equipment, instrumentation) necessary to design, construct
and operate the facility.
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A sulphuric acid with a chemical formula of H2SO4 is a strong acid and it is widely
used for many applications. Sulphuric acid has become one of the most important industrial
chemicals and causing a high demand in sulphuric acid manufacturing locally and globally.
However it is odorless, colorless and extremely corrosive. Sulphuric acid at a high
concentration can cause very dangerous on contact and safety precautions should be strictly
observed when handling it. In general, there are several process in sulphuric acid production
such as contact process, wet sulphuric acid process and others. Among all of the processes,
only contact process are being focused in this mini project.
Now a days, sulphuric acid is prepared by contact process all over the world.
Preparation of sulphuric acid by contact process is based upon the catalytic oxidation of SO2
to SO3.
i. Preparation of SO2.
ii. Purification of SO2.
iii. Oxidation of SO2.
iv. Absorption of SO3.
v. Dilution of Oleum.
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SO2 is obtained by burning sulphur or by heating iron pyrite (FeS2) in pyrite burner.
S + O2 SO2
SO2 contains a number of impurities such as dust particles, Arsenous oxide, vapours,
sulphur etc. These impurities must be removed otherwise catalyst loses its efficiency (catalyst
poisoning).
SO2 is first passed through the dust chamber where steam is spread over the gas to remove
dust particles, which settle down. Fe(OH)3 also sprayed over to remove oxides of Arsenic.
SO2 is then passed through a washing tower after cooling. Here it is sprayed by water to
remove any other soluble impurities.
The gas is now dried by passing through drying tower where concentration H2SO4
(dehydrating agent) is sprayed. H2SO4 removes moisture from SO2.
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Oxidation of SO2 is carried out in contact tower where V2O5 is filled in different pipes. SO2
here reacts with air (O2) to produce SO3. Under above conditions 98% SO2 is converted into
SO3.
2SO2 + O2 2SO3
Oxidation of SO2 is a reversible and exothermic process in which volume of product is less
than the volumes of reactants. In order to obtain maximum amount of SO3, according to Le-
Chateliers Principle following conditions are necessary.
3.3.3.2.1 Temperature
3.3.3.2.2 Pressure
Since volumes of reactants are greater than the product (3:2), therefore, according to Le-
Chateliers Principle a high pressure is favourable. Optimum pressure is about 1.5 to 1.7
atmosphere.
At low temperature, rate of reaction was decreases. To increase rate of reaction a catalyst
vanadium pentaoxide (V2O5) is used.
SO3 is not directly passed in water, because a dense fog of minute particles of H2SO4 is
produced. It is therefore, dissolved in concentrated H2SO4 to form pyrosulphuric acid (oleum).
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In process drawing (Figure 3) sulphur dioxide (SO2) gas having a temperature of 300
to 500 oC generated from roasting furnace is relieved of large-grained dust particles and
impurities by dust Cottrell. Fine dust and impurities that are still not removed are washed off
by the next washing tower and cooled down to 30 to 40 oC through cooling tower. In the
cooled gas a large quantity of mist is present, removed by first mist Cottrell, intermediate
tower and second mist Cottrell. In the gas passed through mist Cottrell, 20 to 40 g/m 3
moisture is contained ; if this is passed on to the next blower heat exchanger, corrosion will be
increased ; so in order to reduce moisture to about 0.1 g/m3, it is dried by a drying tower.
Gas that is dried is passed through a filter by a blower and sent to heat exchanger and
converter. Gas sent into theconverter produces catalytic reaction through catalysis and is
oxidized into sulphur trioxide (SO3). Temperature necessary for catalytic reaction is
constantly maintained by the heat exchanger.
Gas coming out from the converter by way of the heat exchanger is cooled, but is still
too high in temperature (200 oC) for the absorption tower, so it is futher passed through a
cooler to bring the temperture down to 100 oC. Sulphuric acid concentration most suitable for
sulphur trioxide absorption is that point where total vapour tension is minimum; and below
this, concentration component pressure of water will be great, making sulphur trioxide form a
mist with water and difficult to absorb. Sulphur trioxide which has become about 100 oC will
be absorbed by 93.8% sulphuric acid through the absorption tower, and sulphuric acid of 98%
concentration will be produced. In the case of two absorption towers, by circulating fuming
sulphuric acid in the first tower, it will be possible to produce fuming sulphuric acid.
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Figure 3: Process flow diagram (PFD) Contact System Sulphuric Acid Plant
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The process that is selected for the study is involving the reaction in the absorption
tower. The drying acid absorbs the water vapor remaining in the gas after it leaves the Gas
Cleaning Section of the plant. Drying of the gas is necessary:
To avoid corrosion caused by wet SO2 gas before the converter and by wet SO3 after
conversion
To avoid loss of production due to the formation of acid mist in the absorption tower
To keep a clear stack,
To avoid acid condensation during shut-downs and thus protect the catalyst from
degradation
The absorber acid absorbs the SO3 formed in the converter. Absorption of SO3 from the
gas is necessary to:
Remove all SO3 and acid mist from the gas stream before it exits the tower.
Produce 98.5% acid in the absorption tower
The Absorption Towers equipped with a ceramic packing to increase the contact surface
between the SO3 gas and sprayed acid. It is also equipped with mist eliminator to prevent
scabbing of any mist drops from the tower.
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90%
C2 : Concentration of sulfuric acid in 1st stage V2 : Air to bumer control valve
of 2SAR 97% to 99%
C3 : Concentration of sulfuric acid in 2nd stage V3 : SO2 flow control to boiler
of 2SAR 92% to 94%
V4 : Boiler feed water control
Pressure V5 : SO2 flow control to 4SCR
PT1 : AB pressure 0 to 20 kgpcme V6 : Coolant flow control to HE
PT2 : Boiler Pressure 30 to 50 kgpcm2 V7 : Air control for 3rd stage 4SCR
PT3 : Vapor pressure in ACT V8 : Air control for 4th stage 4SCR
PT4 : Vapor pressure in 2SAR V9 : SO3 flow control from 4SCR
V10 : Recycle SO3 flow control for 2SAR
Flow TV1 : Three way valve for vent or recycle of
SO3
F2 : CST to AB flow of sulfur 0 to 10 CFPM V11 : Dilution water control to ACT
F3 : SO2 gas flow to boiler 0 to 10 CFPM V12 : Air control for ACT
F4 : SO2 gas flow to 4SCR 0 to 10 CFPM V13 : Vent control of sulfuric acid vapor
F6 : Sulfuric acid flow from 4SCR to ACT 0
to 10 CFPM
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The Absorbing Acid System absorbs the sulphur trioxide (SO3) that is formed in the
converter to produce sulphuric acid. The reason for absorbing the SO3 is to achieve the
desired production of sulphuric acid and to avoid environmental problems that would result if
the SO3 were allowed to escape to the environment. Efficiently absorbing the SO3 will also
help to maintain a clear stack by avoiding the formation of sub-micron mist particles that
would form the moment the SO3 containing gas leaves the stack and reacts with the moisture
in the air.
a) Absorbing Tower
b) Acid Pump Tank
c) Acid Pump
d) Acid Cooler
e) Piping
f) Instrumentation and Control
An acid pump is required to circulate the acid from the pump tank up to the distributor
inside the Absorbing Tower. The acid flows by gravity over the packing and drain out the
bottom or side of the Absorbing Tower back to the pump tank. The pump can be a vertical
submerged centrifugal pump in which case it would be mounted in the pump tank. External
vertical centrifugal pumps are also available as well as horizontal centrifugal pump types,
although the latter is uncommon.
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An acid pump is required to circulate the acid from the pump tank up to the distributor
inside the Absorbing Tower. The acid flows by gravity over the packing and drain out the
bottom or side of the Absorbing Tower back to the pump tank. The pump can be a vertical
submerged centrifugal pump in which case it would be mounted in the pump tank. External
vertical centrifugal pumps are also available as well as horizontal centrifugal pump types,
although the latter is uncommon.
The absorption of water into sulphuric acid is an exothermic reaction and will cause the
temperature of the acid to rise unless the heat of absorption is removed. The heat is typically
removed in either a plate heat exchanger or anodically protected shell and tube heat
exchanger.
5.1.5 Piping
Acid piping is required to carry the acid from one piece of equipment to the next.
Materials vary considerably depending on the acid concentration, temperature and cost.
Instrumentation and controls are required to monitor the operation of the system and
control its operating parameters. Acid concentration, flow and temperature are the most
important factors in ensuring the system is performing its function of gas drying as efficiently
as possible.
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5.2 Absorption
The absorption of SO3 from the gas relies on equilibrium factors as described in the
section Absorption and Stripping. There are many physical factors that affect the degree of
absorption that will occur in a tower. One of the primary factors is the vapour pressure of
sulphur trioxide/sulphuric acid above the acid.
The vapour pressure curves (better curve to follow) indicate that the lower the acid
temperature, the lower the vapour pressure above the acid. This would imply that operating
the absorber system at lower temperatures would result in better absorption, however, this is
not the case. At lower temperatures other physical properties such as density and viscosity
begin to affect the absorption process in a negative manner.
The specific operating conditions of a plants absorber system will depend on the
design of the tower, packing characteristics, distributor design, acid flow, mist eliminator
efficiency, etc. in addition to the acid concentration and temperature. The optimum operating
conditions can be determined by measuring the amount of SO3/H2SO4 leaving the tower or in
the case of a final absorber, observing the opacity of the stack. The quality of the stack
emissions are observed as the operating conditions are varied. Operating conditions must
reach steady state and be held for a period of time before the affects of the new operating
conditions are recorded. A systematic program of varying operating conditions and
observation will allow the optimum operating conditions to be determined.
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Sulphuric acid (H2SO4) is one of the most important compounds made by the chemical
industry. It is used to make, literally, hundreds of compounds needed by almost every
industry. There are two major processes in production of sulphuric acid, they are by contact
process and lead chambers and it is available commercially in a number of grades and
concentration. The process for producing sulphuric acid has four stages which is extraction of
sulphur, conversion of sulphur to sulphur dioxide, conversion of sulphur dioxide to sulphur
trioxide and conversion of sulphur trioxide to sulphuric acid. The process that is selected for
the study is involving the reaction in the absorption tower. The drying acid absorbs the water
vapor remaining in the gas after it leaves the Gas Cleaning Section of the plant. The absorber
acid absorbs the SO3 formed in the converter. Absorption of SO3 from the gas is necessary to
remove all SO3 and acid mist from the gas stream before it exits the tower. Besides that, it is
to produce 98.5% acid in the absorption tower. The Absorption Towers equipped with a
ceramic packing to increase the contact surface between the SO3 gas and sprayed acid. It is
also equipped with mist eliminator to prevent scabbing of any mist drops from the tower.
Therefore, it is a recommendation for the future process in production of sulphuric acid by
contact process. Firstly, it is about single absorption plant with a tail gas scrubber and bypass
gas direct to tail gas scrubber during extended period of low or no SO2. It is recommended
because single absorption plants are better able to handle varying operating conditions than
double absorption plants. It has lower auto thermal limit than double absorption plants.
Besides that, the tail gas scrubber was able to handle varying inlet SO2 levels and still provide
low SO2 emissions. The tail gas scrubbers are also a backup during startups and upset
conditions. Lastly, acid plants can tolerate short periods of no gas and still retain sufficient
heat in the catalyst to restart without using the preheater. Bypassing gas direct to tail gas
scrubber avoids having to use the preheater to maintain catalyst temperatures.
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7.0 References
Pelletreau, K.; Muller-Parker, G. (2002). "Sulfuric acid in the phaeophyte alga Desmarestia
munda deters feeding by the sea urchin Strongylocentrotus droebachiensis".
Jones, Edward M. (1950). "Chamber Process Manufacture of Sulfuric Acid". Industrial and
Engineering Chemistry 42 (11): 22082210.
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. p. 653.
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