UNIT II: SULFUR AND SILICATES INDUSTRIES

CHEMICAL PROCESS TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING

Dr. B. Krishna Srihari,

Research Assistant Professor,
SRM Institute of Science and Technology,
Krishnasrihari.b@ktr.srmuniv.ac.in
Mob: 9445220677
WisOpt unique id for CPT: 15CH210G248
 Introduction
1. Sulfur Mining (Frasch Process Flow sheet)
2. Manufacture of Sulfuric Acid (Contact Process Flow sheet)
3. Manufacture of Alumina (Bayer’s Process Flow sheet)
4. Ceramic Industries (Short Notes)
5. Glass Industries (Short Notes)
6. Cement rock beneficiation (Flow sheet) and Production of Portland
Cement (Flow sheet)

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 Introduction

 Sulfur is the basic raw material for manufacture of sulfuric acid, which is
considered the barometer of India’s industrial progress.

 Sulfur exists as rhombic crystals, m.p. 112.8 oC and as monoclinic crystals ,

m.p. 119 oC and its boiling point 444.6 oC.

 It is insoluble in water, but soluble in organic solvents and liquid ammonia

 Sulfur exists in the following forms: rock, lump, molten, ground powder and
sublimed powder (flowers of sulfur)
End Uses of elemental sulfur:

 85 – 90 % for sulfuric acid manufacture

 Rest for production of SO2, SO3, CS2, rubber vulcanization agents,

gunpowder, sulfur dyes, putties, sulfur concrete, paper and pulp

Classification of processes:

1. Elemental sulfur mining from salt domes

2. H2S conversion from natural gas and industrial gases

3. Iron pyrites from Amjhore in Bihar state

Raw Materials requirement:

 Sulfur deposits in salt domes

 Large supply of hot water

 Elemental Sulfur Mining by Frasch Process

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Process Description:
 Frasch process is based on the fact that sulfur has comparatively low
melting point
 Its properties allow us to easily extract it from the earth
 A hole is tunneled or drilled in to the deposit and 3 concentric pipes are
placed in hole
 It consists of three concentric pipes includes:
1. One pipe (outer most pipe ) carries super heated water at 160 – 180 oC in to
the sulfur bed
2. Another pipe (middle of the pipe) carries compressed air under pressure at
20-25 atm
3. Last pipe is used to carry sulfur back to the surface
Process Description continued:
 Super heated water is used to melt the solid sulfur in a sulfur bed
 Compressed air is used to increase the pressure of the deposit forcing sulfur
– water mixture to the surface
 On cooling, about 99% pure sulfur solidifies and is collected in bins.
 Before collecting or storing the sulfur, if any impurities present are
separated firstly by using a phase separator unit.
 The remaining trace amount of impurities separated by pressure filter
 Finally after separating all the impurities, pure form of sulfur stored in a
solidification vats in the form of solid sulfur.
 If you wants to store sulfur in molten state, use spherical storages in which
heating coils provided to maintain a sulfur in a molten state.
 Manufacture of Sulfuric Acid by
Contact Process

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 Manufacture of sulfuric acid
 Sulfuric acid (H2SO4) is a highly corrosive strong mineral acid.
 It is a colorless to slightly yellow viscous liquid which is soluble in water at all
concentrations.
 It is one of the most important heavy industrial chemicals due to it has a number
of large-scale uses particularly in the phosphate fertilizer industry.
 About 60 % of the sulfuric acid produced is utilized in fertilizer manufacture.
 Sulfuric acid was called "oil of vitriol" by Medieval.
 More sulfuric acid is produced than any other chemical in the world.

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 Manufacture of sulfuric acid
 Classification of Processes
1. The Lead Chamber Process
2. The Contact Process
 Both processes are based on SO2.
 Chamber Process was developed first in 1746.
 But produced acid of concentration less than 80%.
 Contact process yields 98% H2SO4 and higher which can be diluted, if
necessary.
 Chamber process is virtually obsolete.
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Manufacture of sulfuric acid by CONTACT PROCESS

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 Process Description
Sulfuric acid is commonly prepared by the contact process. There are five steps
involved in the manufacture of sulfuric acid by the contact process. They are
1. Production SO2 from sulfur (Burning) S + O2 → SO2

2. Purification of Sulfur dioxide To remove dust particles,

oxides of iron and arsenic etc.,
V2O5
3. Catalytic oxidation of SO2 to SO3 2SO2 + O2 → 2SO3 + Heat

4. Absorption of SO3 in 98% H2SO4 to produce Oleum SO3 + H2SO4 → H2S2O7

5. Absorption of SO3 in 97% H2SO to produce 98% SO3 + H2O (97% H2SO4) → H2SO4

H2SO4
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Figure: Manufacturing of Sulfuric Acid and Oleum by Contact Process

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Manufacture of Sulfuric acid and oleum by contact process
 Process Description Cont.…
 The liquefied and purified sulfur fed in to the burner and dried air also supplied
to the burner by an air blower or compressor through a drying tower.

 The gases coming out from the burner are at temperature of 950–1,000 °C and
contain 10.0–10.5% sulfur dioxide.

 They are passed through a waste heat recovery boiler where high pressure steam
is produced while the gases are cooled to 390–410 °C depending on the plant
design.

 If the mixture of SO2 and air contains impurities, which must be removed.
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 Process Description Cont.…
 Otherwise the catalyst loses its efficiency.
 They are dust particles, pyrite dust and arsenic oxide etc.
 Then the mixture is passed through a dusting tower in which solid particles
removed
 Scrubbing tower where complete removal of dust particles
 Drying tower where mixture is dried with sulfuric acid and
 Arsenic purifier where every trace of arsenic oxide is removed.

 The purified air-SO2 gas mixture containing 7-10% SO2 and 11-14% O2 is
preheated if necessary, and sent to first stage of two stage catalytic converter.

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 Process Description Cont.…
 This is high temperature (500-600 oC) stage, contains 30% of total catalyst and
converts about 80% of SO2.

 The converter product is cooled by heat exchange at 300oC and fed to a second
stage where total yield is increased to 97% by operating at 400-450 oC for
favorable equilibrium.

 High yield product gas (SO3) is cooled to 150 oC by water and air heat
exchangers and absorbed in Oleum fed at a rate to allow not over a 1% rise in
acid strength in a first absorption (Oleum absorption tower) tower.

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 Process Description Cont.…

 The remaining gas from Oleum absorption tower scrubbed with a

lower strength of 97% sulfuric acid in a second absorption (H2SO4
absorption tower) tower.
 Oleum concentrations up to 40% can be made by tower
absorption.

 Higher strength Oleum up to 65% is prepared by distilling 20%

Oleum.
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 Advantages of V2O5 catalyst

1. Relatively immune or protect to poisons (such as As, Cl or F)

2. Low initial investment and only 5% replacement per year

3. For 1 ton of 100% sulfuric acid production only 10-14 kg of V2O5

(in which 7-8% of V2O5 is present) is sufficient.

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 Disadvantages of V2O5 catalyst

1. Must use dilute SO2 input (7-10%), at higher concentrations of

SO2 catalyst is less active and requires high O2/SO2 ratio to give

economic conversion.

2. Larger converters and higher initial investment are necessary.

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 Main Uses of H2SO4

 Fertilizer Industry: Producing phosphate fertilizers

 Producing ammonium and potassium sulphates

 Dehydrating agent

 Oil refining

 Metal process industry: mainly for pickling process

 Extraction of copper, uranium and vanadium from ores

 Production of TiO2

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 Major Engineering problem

 Design of multistage catalytic converter for a highly exothermic reaction

 Optimization of space velocity in catalyst chamber

 Pumping cost and fixed charges of process equipment

 Optimization studies show that equilibrium yield can be increased by square

root of system pressure PT at a given temperature.

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Catalyst: V2O5: Most widely used catalyst is V2O5 dispersed on a porous carrier in
pellet form. Platinum (Pt) catalyst was previously used but suffers from easy
poisoning, fragility, rapid heat deactivation, and high initial investment.
Characteristics of catalyst:
1. Porous carrier: Having large surface area, controlled pore size and resistance
to process gases at high temperatures. In pellet form used in fixed beds and
powder form used in fluidized beds. Example: Alumina, silica gel, kieselguhr
(acts as filter, filler or insulator), Diatomaceous earth, Zeolite etc.
2. Active catalyst agent: Adding water soluble compounds to gels or porous
substrates and firing at temperatures below sintering point will increase the
strength of the material.
3. Promotor: Alkali and/or metallic compounds added in trace amounts to
enhance activity of catalyst.
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• Roasted: Heating at higher temperature’s
• Pickling: Pickling is a metal surface treatment used to remove impurities, such
as stains, inorganic contaminants, rust or scale from ferrous metals, copper,
precious metals and aluminum alloys. A solution called pickle liquor, which
contains strong acids, is used to remove the surface impurities.
• Stripping: Stripping is a physical separation process where one or more
components are removed from a liquid stream by a vapor stream. Stripping is
usually carried out in either a packed or tray column.
• Fragility: Easily broken or damaged
• Sintering point: It is a heat treatment applied to a powder or solid component
in order to impact strength and integrity
• Space velocity: How many reactor volumes of feed can be treated in a unit
time. Space velocity refers to the volumetric flow rate of the reactants divided
by the reactor volume or the catalyst bed volume.
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Purification of Alumina from Bauxite by
Bayer Process
Raw Material:

• The only raw material is Bauxite which contains 50-60% Al2O3 ore,
remaining balance silica and Iron ore, which is transported from nearby
Indian deposits.

• Minor quantities of make-up sodium hydroxide are required.

Chemical Reactions Involved

1. 6NaOH + Al2O3 → 2Na3AlO3 + 3H2O

2. Na3AlO3 + 3H2O → 3NaOH + Al(OH)3

3. 2Al(OH)3 → Al2O3 (Purified) + H2O

Purification of Alumina from Bauxite by Bayer Process
S.No. Process Unit Operation/Process and Discussion
Equipment
1 Size Reduction 1. Size reduction
Equipment 2. Produce 2-5 cm lump size of bauxite with Jaw crusher
3. Then wet ground to -100 mesh with ball mill or Tube
mill
2 Mixer 1. Mixing
2. NaOH + bauxite mixing takes place
3. NaOH from recycle stream used and if required small
quantity of NaOH make-up
3 Autoclave 1. Reaction
Digester 2. Operating at 4.5 atmosphere
3. NaOH and bauxite reaction takes place as per following
6NaOH + Al2O3 → 2Na3AlO3 + 3H2O
4. Then fed into a series of four counter current thickeners
4 Series of Four 1. Settling
Counter current 2. Here sodium aluminate separated from silica and iron
thickeners ore which are precipitated at the bottom
3. The slurry is washed with hot water in counter current
thickeners
4. The thickened slurry called red mud is separated from
the bottom as a waste or sent for recovery
5 Rotary Filter 1. Filtration
2. The supernatant sodium ortho aluminate (Na3AlO3)
from overflow of the series of thickeners pass through a
rotary filter
3. Here, again wash the sodium ortho aluminate with
water by removing traces of impurities present in the
solution
6 Precipitator or 1. Crystallization or Precipitation
Crystallizer 2. The diluted mixture from rotary filter is cooled and
seeded in a crystallizer by adding seed crystals of
Al(OH)3 to induce crystallization of the trihydrate.
According to the following reaction
Na3AlO3 + 3H2O → 3NaOH + Al(OH)3
7 Series of Three 1. Settling
Counter current 2. The crystallized slurry matrix is fed to another set of counter
thickeners current thickeners where all of the NaOH is removed from over
flow or top of the thickeners by adding hot water continuously
3. The bottom product [Al(OH)3] from thickeners is moved to a
calciner through rotary filter where maximum possible NaOH
and water separated.

8 Calciner 1. Heating
2. The product from the thickeners heating to 1100 OC, drives
off water of hydration plus excess water as per the following
reaction
2Al(OH)3 → Al2O3 (Purified) + H2O
3. The purified alumina or aluminum from calciner cooled and
shipped to Electrolytic reduction plant to produce Aluminia.
9 Multiple effect 1. Evaporation
Evaporator 2. The dilute caustic solution from second set of
thickeners is concentrated in a multiple effect evaporator
system and recycled.

USES:
 90% used as Electrolytic reduction plant for production of Aluminia or
Aluminium
 Chemical and Refractory Industries
Thank you