Inorganic Industries Engineering

‫هندسة الصناعات غريالعضويه‬

Lecture 2
Dr.: Sameh Araby El-Mekawy
 Introduction
It is referred as universal chemical, king of chemicals due to its
numerous applications as a raw material or processing agent.
 It is the most commonly used chemical in the world and used in
almost all industries like
 Fertilizers  Steel manufacturing
 Pharmaceuticals  Cellulose fibers
 Paper bleaching  Coloring agents
 Sugar bleaching  Sulfonation agents
 Gasoline  Amino acid intermediates
 Automobile batteries  Regeneration of ion exchange resins
 Water treatment
Worldwide Production
Sulphuric acid is an important industrial chemical which is used in
the manufacturing processes of many goods over a wide range of
applications.

Over one million tons of sulphuric acid is made each year in the
UK alone, with an additional 40 million tones being produced in
the USA.

Annual worldwide production of sulphuric acid is stands at around

180 million tones.
Raw Materials
 Sulphur (S)
 Air
Sources of Sulphur
 Sulfur is the 10th most common element in the universe.
 Sulfur exists in nature as elemental deposits around volcano vents. as
well as sulfides of iron [ pyrite], zinc [sphalerite], lead [galena], and
mercury [cinnabar] and in the form of sulfates of calcium
[gypsum CaSO4.2H2O], barium [barite BaSO4].
 There are two principle sources of sulfur in the manufacture of sulphuric
acid
 Sulfur from mines
 Sulfur or hydrogen sulfide H2S recovered from petroleum desulfurization
Sulfur Extraction
(1) Sulfur mining (Frasch process)
(2) Claus Process
The Frasch process is a method to extract sulfur from
underground deposits. It is the only industrial method of
recovering sulfur from elemental deposits. Most of the world's
sulfur was obtained this way until the late the last century, when
sulfur recovered from petroleum and gas sources became more
commonplace.
Process description
 In the Frasch process, three concentric tubes are introduced into
the sulfur deposit. Superheated water (170 °C, 1.5 MPa) is
pumped into the deposit via the outermost tube. Sulfur
(m.p. 115 °C) melts and flows into the middle tube. Water
pressure alone is unable to force the sulfur into the surface due to
the molten sulfur's greater density, so hot air is introduced via the
innermost tube to froth the sulfur, making it less dense, and
pushing it to the surface.
The sulfur obtained can be very pure (99.7 - 99.8%). In this form,
it is light yellow in color. If contaminated by organic compounds,
it can be dark-colored; further purification is not economic, and
usually unnecessary.
The Frasch process can be used for deposits 50–800 meters deep.
3-38 cubic meters of superheated water are required to produce
every tone of sulfur, and the associated energy cost is significant.
Properties of Sulfur allowing Extraction
 Low melting point of roughly 115 C due to weak dispersion forces
(super heated water melts this easily).
 Low density (2.07g/cm3) forms a sulfur-water emulsion that is light and
can be readily transported to the surface with compressed air.
 Because sulfur is insoluble in water, when the steam melts sulfur, it can
not dissolve in water and therefore it makes it easier to separate once
out of the deposit and allows it to be collected on the surface). Inert,
non-toxic and non-volatile, meaning no special precautions are required
to protect health of miners.
Environmental impacts of Frasch process includes :
 Thermal pollution from superheated steam: Recovered water
contains some dissolved minerals. The effluent need to be cooled
to avoid thermal pollution and should be recycled to avoid
contamination of local ecosystems.
 Earth subsidence: removing the sulphur may result in ground
instability for that area
 Production of unwanted by products: Can produce sulphur
dioxide (acid rain) and hydrogen sulfide (Hydrogen sulfide is a
smelly (with its signature "rotten egg" smell), corrosive, and toxic
gas.
Schematic of Frasch Process
(2) ClausProcess
 “Claus Process” is used to convert the sulphur compounds in
sour gas to elemental sulphur. This process, invented by English
scientist C. F. Claus, is now the most widely used method for
extraction of sulphur from sour gas.
Approximately 90 to 95 percent of recovered sulfur is produced
by the Claus process.
Hydrogen sulfide, a byproduct of crude oil and natural gas
processing, is recovered and converted to elemental sulfur by
the Claus process.
H2S is a smelly, corrosive, highly toxic gas, which also
deactivates industrial catalysts. Therefore it is converted to non-
toxic and useful elemental sulfur at almost all locations where it
is produced.
Schematic of modified Claus Process
 Process description
Modified Claus process comprise two conversion stages: thermal
conversion stage and catalytic conversion stages.
(1) Thermal step
The H2S containing gas is fed to the Thermic Converter where it is
partially oxidized with air in a reaction furnace at high temperatures
(1000 to 1400 °C). Combustion air is fed to the burner, with the
amount of air controlled to combust only 1/3 of the H2S to
SO2according to chemical reaction below:
2H2S + 3 O2 → 2SO2 + 2H2O+heat
 Then, the remaining uncombusted 2/3 H2S reacts with the SO2,
producing Elemental sulfur according to following chemical
reaction:
2H2S + SO2 ↔ 3S + 2H2O+heat
The global Claus process chemical reaction is represented below:
3H2S + 3/2 O2 ↔ 3S + 3H2O
 The hot combustion products from the furnace enter the waste
heat boiler and are partially cooled by generating steam. The gas
is further cooled in the first sulfur condenser, to condense the
sulfur formed in the furnace, which is then separated from the
gas and drained to a collection pit.
 The gas leaving the sulfur condenser is heated again to avoid
forming liquid sulfur in the downstream catalyst bed and enters
the first catalytic converter.
Usually, 60 to 70% of the total amount of elemental sulfur
produced in the process are obtained in the thermal process step.
(2) Catalytic step
 The Claus reaction continues in the catalytic step with activated
aluminum(III) or titanium(IV) oxide, and serves to boost the sulfur yield.
2 H2S + SO2 3 S + 2 H2O (ΔH = -1165.6 kJ mol-1)
 The catalytic conversion is usually carried out in a multi-stage fixed-bed
adsorptive reactors process, to counteract the severe equilibrium limitations at
high conversions. Because this reaction represents an equilibrium chemical
reaction, it is not possible for a Claus plant to convert all the incoming sulfur
compounds to elemental sulfur. Therefore, 2 or more stages are used in series to
recover the sulfur.
 This technology process can possibly provide about 96-98% conversion of the
influent sulfur in H2S to S.
 Each catalytic stage consists of a gas reheater, a catalyst chamber, and a
condenser
 The first process step in the catalytic stage is the gas heating process. It is
necessary to prevent sulfur condensation in the catalyst bed, which can lead to
catalyst fouling. The required bed operating temperature in the individual
catalytic stages is achieved by heating the process gas in a reheater until the
desired operating bed temperature is reached.
Catalytic step (continued)
 The catalytic conversion is maximized at lower temperatures , but care
must be taken to ensure that each bed is operated above the dew point of
sulfur (120–150 °C) to avoid liquid sulfur physically deactivating the
catalyst.
Catalytic stage Operating temperature oC
1 305
2 225
3 200

 The tail gas, containing H2S, SO2, sulfur vapor, and traces of other
sulfur compounds formed in the combustion section, escapes with the
inert gases from the tail end of the plant. Thus, it is frequently necessary
to follow the Claus unit with a tail gas cleanup unit to achieve higher
recovery.
Manufacture of sulphuric acid
 The manufacture of sulphuric acid is carried out by two processes:
1. The Lead Chamber process
2. The Contact process.
1) Lead Chamber Process:
 The lead chamber process was an industrial method used to produce
sulfuric acid in large quantities.
 It is used for producing sulfuric acid by oxidizing sulfur dioxide with
moist air, using gaseous nitrogen oxides as catalysts (Carrier catalyst).
 The gases are sprayed in the chamber with Lead metal sheets. The
sulfur dioxide and nitrogen dioxide are allowed to react for 30 minutes
as the sulfur dioxide is oxidized to sulfuric acid.
S + O2 → SO2
SO2 + NO2 →SO3 + NO
SO3 + H2O→ H2SO4
NO + O2 →2NO2
 Sulphuric acid produced in this way is only about 62 to 70 % H2SO4.
The rest is water. The chamber process has become obsolete and has
been replaced by the contact process due to the following reasons:
i. An increased demand for strong, pure acid and oleum
ii. Contact process plants are cheaper and more efficient
2) Contact Process
 The contact process is the current method of producing sulfuric
acid in the high concentrations needed for industrial processes.
Vanadium(V) oxide is the catalyst employed.
 The contact process was introduced as a far more economical
process for producing sulphur trioxide and concentrated sulfuric
acid than the previous lead chamber process method used for
producing sulfuric acid.
 In the contact processes, the sulfur dioxide is converted to sulfur
trioxide by the use of metal oxide catalyst.
 In England, 1831, a patent was filed that described the oxidation of
sulfur dioxide over a platinum catalyst, the Contact Process. This
new process increased yields of reaction from 70 to above 95%.
 Pt Catalyst because of it’s excessive first cost and susceptibility to
poisoning, it has been largely replaced by vanadium oxide.
 In 1913 BASF was granted a patent for the use of vanadium
pentoxide as a catalyst for the Contact Process
 By the 1930’s vanadium pentoxide was becoming the dominate
catalyst used because of insensitivities to poisons and lower cost.
 In 1960 a patent application was filed by Bayer using the so called
double-catalyst process (double absorption).
Contact process

Process flow diagram of contact process

 Essentially all sulfuric acid today is manufactured by the contact process
Process outlines
The main steps in the contact process are:
1) sulphur powder is melted and burned in presence of oxygen to produce
sulphur dioxide gas.
2) purifying and cooling the gas
3) Catalytic oxidation of SO2 to SO3 (the heart of the process)
4) Absorbing the sulphur trioxide in sulphuric acid in oleum tower,
5) Water is added to the acid tank to produce H2SO4 by reacting with
oleum.
Burning of sulfur
 The first step is to spray molten sulfur
under pressure into a furnace up to
1000°C.
 Here is burns in air to produce sulfur
dioxide gas. SO2 gas is then cooled for
the next step
S(l) + O2(g) → SO2(g) ∆H = -297 kJ mol-1

 The heat from the hot gases recovered

to produce steam in a boiler.
 Air and liquid sulphur are fed into the
furnace via a sulphur gun equipped
with an atomizing spray nozzle or a
rotary cup burner.
 The high surface area of the sulfur
spray allows combustion to be rapid.
Purification unit
 This includes the dusting tower, cooling pipes, scrubbers, drying tower,
arsenic purifier and testing box. Sulfur dioxide has many impurities such
as vapours, dust particles and arsenous oxide.
 Therefore, it must be purified to avoid catalyst poisoning (i.e.:
destroying catalytic activity and loss of efficiency).
 In this process, the gas is washed with water, and dried by sulfuric acid.
In the dusting tower, the sulfur dioxide is exposed to a steam which
removes the dust particles.
 Dust is removed from the gas by a series of electrostatic precipitation
and scrubbing steps.
 A scrubber is a device used to remove chemicals and solids from
process gases. Scrubbers are cylindrical and can be filled with
packing material or left empty. As dirty gases enter the lower
section of a scrubber they begin to rise. As these dirty vapors rise,
they encounter a liquid chemical wash that is being sprayed
downward. As the vapors and liquid come into contact, the
undesirable products entrained in the stream are removed. As the
dirty materials are absorbed into the liquid medium, they fall to the
bottom of the scrubber, where they are mechanically removed.
Clean gases flow out of the top of the scrubber and on for further
processing.
 After the gas is cooled, the sulfur dioxide enters the washing tower
where it is sprayed by water to remove any soluble impurities.
 In the drying tower, sulfuric acid is sprayed on the gas to remove
the moisture from it. It has been found in practice that if moisture
is present in the gases before conversion, a sulfur trioxide mist will
form after the converters, which is extremely difficult to absorb in
the acid absorbers.
 Finally, arsenic oxide is removed when the gas is exposed to ferric
hydroxide.
Catalytic oxidation of SO2 to SO3
 Four converters filed with catalyst are arranged in series where
oxygen and sulphur dioxide are reacted to form sulphur trioxide

2SO2(g) + O2(g)↔ 2SO3(g); ∆H = -197 kJ mol-1

 Because the reaction is exothermic it is necessary to cool the gas

mixture as it passes from one tray to another to maintain the desired
reaction temperature. Heat produced from the reaction is removed by
the heat exchanger arranged in between them. The catalyst used is
vanadium pentoxide (V2O5) at 1.2-1.5 atm. The temperature has to be
kept around 450oC. If it rises above 450oC, the equilibrium is displaced
away from SO3. Temperature should reach around 450oC for the
catalyst to be activated.
 Absorption of SO3
 Sulfur trioxide reacts with water to form sulfuric acid:
SO3(g) + H2O(l) → H2SO4(aq); ∆H = -130 kJ mol-1
However direct reaction with water is not used, because so much heat
evolves when sulfur trioxide is added to water that a fine mist (fog) of acid
is produced which is difficult to collect.
 Instead, SO3 gas is passed into Conc. sulfuric acid in an absorption
tower. This reaction occurs in two steps
1. The sulfur trioxide gas dissolves almost totally in the acid to form a
liquid known as fuming sulphuric acid or Oleum
SO3(g) + H2SO4(l) → H2S2O7(l)
2. Oleum obtained from the absorption tower is then carefully mixed with
water to produce sulfuric acid: H2S2O7(l) + H2O(l) → H2SO4(l)
Mixing of Oleum with water
Add oleum to water slowly, why?
The reaction is strongly
exothermic so the mixture will
bubble and boil spitting acid out
of the container
By adding water to oleum
because the oleum is denser than
water the reaction will only
occure on the surface allowing
more acid to spill out
The efficiency of the absorption depends on the following:
• H2SO4 concentration of the absorbing liquid (98.3–98.7%)
• Range of temperature of the liquid (normally 70 °C–120 °C)
• The heat of absorption being removed by the Heat Exchanger
• Moisture content in the raw gas which can produce fine acid mist particles,
which are very difficult to absorb
• An acid mist filter to arrest the mist of sulfuric acid in the system
• Temperature of incoming gas
The strategy followed to maintain high conversion and reaction
rate in converter:
(1) Design: The design and operation of sulphuric acid plants are
focused on the following gas phase chemical reaction in the presence of a
catalyst: 2SO2(g) + O2(g)↔ 2SO3(g); ∆H = -197 kJ mol-1

Inlet and outlet stream temperature control by intermediate heat exchanger

approach value to obtain maximum conversion:
Catalyst
 Without a catalyst this reaction needs a very high temperature to have
a realistic rate. The equilibrium is however in favour of SO2 -
formation at higher temperatures which makes the conversion very
poor.

 The main steps involved in the rate of contact reactions in

heterogeneous catalyst are as follows

Diffusion of the reacting gases to the catalyst

Adsorption of the gases on the surface of the catalyst
Chemical reactions taking place on the surface of the catalyst
Desorption of the reaction products from the surface of the catalyst
Diffusion of the reacted molecules away from the catalyst
Comparison of vanadium and platinum catalyst
(2) Reaction conditions
2SO2(g) + O2(g)↔ 2SO3(g); ∆H = -197 kJ mol-1

Temperature
 The forward reaction (the production of sulphur trioxide) is
exothermic.
 According to Le Chatelier's Principle, this will be favoured if you
lower the temperature. The system will respond by moving the
position of equilibrium to counteract this - in other words by
producing more heat.
 In order to get as much sulphur trioxide as possible in the
equilibrium mixture, you need as low a temperature as possible.
However, 400 - 450°C isn't a low temperature!
Pressure
 According to Le Chatelier's Principle, if you increase the pressure the
system will respond by favouring the reaction which produces fewer
molecules. That will cause the pressure to fall again.
 In order to get as much sulphur trioxide as possible in the equilibrium
mixture, you need as high a pressure as possible. High pressures also
increase the rate of the reaction. However, the reaction is done at
pressures close to atmospheric pressure!
Economic considerations
 Even at these relatively low pressures, there is a 99.5% conversion of
sulphur dioxide into sulphur trioxide. The very small improvement
that you could achieve by increasing the pressure isn't worth the
expense of producing those high pressures.
Environmental aspects
The main pollutants emitted are:

 SO2 resulting from the uncompleted character of the reaction of

oxidation

 SO3 resulting from the uncompleted absorption of SO3

 droplets of H2SO4 resulting from absorption

 H2SO4 vapour from scrubbing.

 Storage
- 98% sulfuric acid is virtually all molecular (very few ions).
- It does not attack iron and steel, so can safely be stored in steel
containers or transported in steel tankers.
- Steel has greater strength than glass and plastic containers.
- However, diluted sulfuric acid contains hydrogen ions and vigorously
attacks metals such as iron and steel. Hence diluted acid must be stored in
glass or plastic containers. This is more difficult to transport.
- When storing or transporting this acid in steel containers, care must be
taken to avoid contamination with water, because that could set off a
vigorous reaction b/w the acid and the container.
Top industries use sulfuric acid
 The fertilizer market is the largest U.S. single use for sulfuric acid and
consumes 50-65 percent of all produced.
 Mostly in production of phosphoric acid, which in turn used to
manufacture fertilizers such as triple superphosphate, mono and
diammonium phosphates
 Used in the organic chemical industry. Production of plastics and
synthetic fibers are examples.
 Production of TiO2 consumes large quantities of sulfuric acid. TiO2 is
a white pigment used in paints and plastics.
 In the metal industry sulfuric acid is used for pickling ferrous and
non-ferrous materials and in the recovery of copper, nickel, and zinc
from low-grade ores.
 Finally, the petroleum industry uses acid as a catalyst for various
reactions.
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