ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)

LECTURE NOTES
Course synopsis
A. The manufacture of Glass, Ceramics, and Binding materials.
Synthesis gas
Water gas
Oxo process (Hydroformylation)
B. Industrial Processes involving:
(1) Oils and Fats
(2) Soaps
(3) Detergents
C. Wood pulp and paper
Fibre materials
TYPES OF GLASS AND THEIRCOMPOSITION

DEFINITION

Glass is an amorphous, hard, brittle, transparent or translucent supercooled liquid of infinite

viscosity, having no definite melting point obtained by fusing a mixture of some metallic
silicates or borates of Sodium, Potassium, Calcium and Lead.
The most familiar and historically the oldest types of manufactured glass are “Silicate glasses”
based on the chemical compound silica, the primary constituent of sand. As per ASTM
(American Society for Testing and Materials) standard for glass:- “Glass is an inorganic product
of fusion which has been cooled to a rigid condition without crystallization.”

RAW MATERIALS USED IN THE MANUFACTURING OF GLASS

Sodium as Na2CO3 (used in soft glass)

Potassium as K2CO3 (used in hard glass)
Calcium as limestone, chalk and lime.
Lead as litharge, red lead (flint glass)
Zinc is zinc oxide (heat and shockproof glass)
Borates are borax, Boric acid (heat and shockproof glass
CLASSIFICATION OF GLASS

Glass

Page | 2

Non-Oxide Glass Oxide Glass

Soda-Lime-Silica Silicate Glass Non-Silicate Glass

Glass

Non-Oxide Glass
These are glasses that do not contain oxygen.
Heavy metal fluorides: Fluorides of Zr, Ba, La, Al, Na (ZBLAN). They are used in
telecommunication fibres (because they have relatively low optical loss). They are extremely
difficult to form and have poor chemical durability.
Glassy metals (no oxide metals): They are formed by high-speed quenching of fluid
metals. Examples are compounds of iron, nickel, phosphorus and boron. They are used in
flexible magnetic shielding and power transformers. Semiconducting solids (Chalcogenides):
Chalcogenides are noted for their superior electronic, optical, and semiconducting properties.
Chalcogens are the chemical elements in group 16 of the Periodic Table.

This group is also known as the oxygen family; Group 16 consists of the elements oxygen (O),
sulphur (S), selenium (Se), tellurium (Te), and the radioactive elements polonium (Po) and
livermorium (Lv).
They are formed by melting together S, Se, or Te with elements of group15 and 14 (As, Sb, Ge).
They are used in threshold and memory-switching devices and in xerography.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Amorphous silicon (Si) and amorphous germanium (Ge) are used in photovoltaic applications,
solar cells, and calculators.
Oxide Glass
Non-silicate glasses: These are glasses not containing silica (SiO ). Generally, they are
2
phosphates and borates.

Silicate glasses: These are glasses that are based on silica, and are referred to as Vitreous
Silica.
Silicate glasses are used in high service temperatures.
They have very high thermal shock resistance
They have high chemical durability
Very low electrical conductivity
Good Ultra-violet light transparency
Soda-lime-silica-based glasses: These are low-cost, good-durability glasses used in
containers, window planes, light bulbs and tubes, Table wares, etc.

PROPERTIES OF GLASS

The random arrangement of atoms is responsible for many of the properties that distinguish
glass from other solids.
One unique property of glass is its isotropicity (its physical properties are the same in all
directions). That is properties such as tensile strength, electrical resistance, refractive index,
thermal expansion, etc., do not vary with direction. They are of equal magnitude in any
direction throughout the material.
Density: In the random atomic order of a glassy solid, the atoms are packed less densely than
in a crystalline solid. This random arrangement leaves large interstitial spaces or holes between
the atoms. The density of glass depends on the composition.
Elasticity and Plasticity: Elasticity is a measure of the ability of a solid to recover its original
dimensions after being subjected to lengthwise tension or compression. Glasses have high
elasticity.

Thermal Properties:

The thermal properties of glass are characterized by transformation temperature (Tg), sag
temperature (Ts ), annealing point (T1013), softening point (T107.6), mean coefficient of linear
thermal expansion ( α ,α ), Thermal Conductivity (λ) and specific heat capacity
-30/+70ºC 100/300ºC
(C )
p

The viscosity of glass depends on temperature.

The viscosity of glass decreases with a temperature rise (it is measured in Poise (cm g s).
The transformation of glass from liquid state to solid state is gradual.

The transition takes place over a range of temperatures called the Glass Transformation range
called Glass Transition Temperature (T ).
g
The addition of alkali (network modifier) lowers the transformation temperature.

Thermal Expansion

• Glass expands when heated and shrinks when cooled.

• When hot and glass is suddenly cooled, the outer layer shrinks relative to the
inner layer.
• Great tension may develop in the outer layer leading to cracking.
Resistance to such thermal shock is called Thermal Endurance of Glass.

Thermal Expansion
• It is inversely proportional to the thermal expansion coefficient and thickness of
the glass.
• Soda-lime silicates and alkali-lead-silicates have high thermal expansion
coefficient. Page | 4
Pyrex-type sodium borosilicates and vitreous silica have low thermal expansion coefficient
Silica glass containing 7.5 % TiO has zero thermal expansion coefficient.
2

Thermal Conductivity

Thermal conductivity is a property of atomic vibration.

Atomic vibration does not increase appreciably with temperature, hence glass has low thermal
conductivity.

Chemical Properties
• The chemical durability of glass depends on an ion exchange reaction in which
alkali ions in the glass are exchanged with hydrogen atoms or hydronium ions
present in the atmospheric humidity or water.
• The alkali metal ions thus leached out of the glass react with CO2 and H2O in the
atmosphere to produce alkali carbonates and bicarbonates (which deposit on the
glass surface).
• Vitreous silica, borosilicate, and aluminosilicates have excellent weathering
resistance.
 Small amounts of alumina in glass improve the chemical durability of glass.

Electrical Properties

Electrical conductivity
• Although most glasses contain charged metal ions capable of conducting
electricity, the high viscosity of the glass prevents their movements and prevents
electrical conductivity.
• Thus glass is an efficient electrical insulator.
• High voltage lamps require low electrical conductivity glass
Dielectric Constant
• Glasses have a high dielectric constant.
• The dielectric constant of glass increases generally with the concentration of
Network Modifying (NWM) ions.
• Most soda-lime-silicate glasses have a high dielectric constant.
• They are used in separating plates of capacitors, and in Ics.
• Vitreous silica has the lowest dielectric constant.

Optical Properties

Transparency
• Electrons in glass molecules are confined to particular energy levels.
• They cannot absorb and reemit photons (no electronic transitions).
• Consequently, light energy travels through glass without absorption and
reflection.
• Therefore, glass is transparent.
• Molecular units in glass are smaller than the wavelength of ordinary light, hence
the absorption of light is negligible.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Opacity
• Radiation of some wavelengths can cause glass molecules to vibrate, making the
glass opaque.
• For example, most oxide glasses are opaque to UV radiation (< 350 nm).

Colour
A glass containing certain metallic oxide absorbs the wavelength of a certain colour
•
and lets other wavelengths pass, thus the glass appears coloured.
• For example, Cobalt oxide gives a blue colour to glass; chromium oxide gives a
green colour; manganese oxide gives a purple colour.
Photosensitivity
• Glass containing a small amount of cerium oxide and ions of copper, silver or gold
when exposed to UV radiation causes the oxidation of cerium and reduction of
copper, silver or gold ions to a metallic state.
• Upon subsequent heating, the metal nuclei grow to a colloidal state and develop
colour (Red for copper and gold, yellow for silver).

Photosensitivity
• Photochromic eyeglasses are generally alkaliboroaluminosilicates with 0.01 to 0.1
% silver halide and a small amount of copper.
• Upon absorption of light, the silver ion reduces to metallic silver and forms a
colloid about 120 Å in size.
• The colloid makes the glass grey or brown.
• This darkening is removed by the removal of the light (optical bleach) or by raising
the temperature (thermal bleaching).
Refraction and Reflection of Light

When a light ray strikes the boundary between two mediums at an angle other than the normal
angle, the light will be partially reflected back into the first medium and partially refracted or
deflected in its path through the second medium.

The effect of light reflected or refracted depends on the relative densities of the two mediums
(glass and air) and also depends on the angle of incidence.
If 𝜃𝑖 < 𝜃𝑐 most of the light is refracted and a small amount is reflected.

If 𝜃𝑖 > 𝜃𝑐 all the light is reflected to the glass.

The refractive index depends on the type of glass and wavelength of light
Types of Glass

1. Sodalime or soft Glass

2. Borosilicate / pyrex / Jena Glass
3. Lead Glass or Flint Glass
4. Aluminosilicate Glass
5. Toughened Glass Page | 6
6. Potash lime or hard Glass
7. Wired Glass
8. Coloured Glass
9. Laminated Glass

1. Soda-lime or Soft Glass

About 90% of all glass is soda-lime glass made with silica (sand), Carbonate and soda ash.
The approximate composition is [Link].6SiO2. They are low-cost, and resistant to
water water but not to acids. They can melt easily and hence can be hot-worked.

Composition: The composition of soda-lime glass varies marginally depending on the

manufacturer. The typical composition of soda-lime glass is 73% SiO2 – 15% Na2O − 7% CaO −
3
4% MgO − 1% Al2O3 Refractive index - 1.46 Density, 2.5 ρ (g/cm )

Uses: Window glass, Electric bulbs, Plate glass, Bottles, Jars, Cheaper tableware, Test tubes,
Reagent bottles etc.

2. Borosilicate / Pyrex / Jena Glass

 It is a common hard glass containing silica and boron with a small amount of
alumina and less alkaline solids.
 These equipments are mainly known for being resistant to thermal shock as
compared to other ordinary glasses.
 The borosilicate glass is made by adding the boric oxide to the traditional
glassmaker frit of the silicate soda, sand or the ground lime.
 The glass normally requires a higher temperature to melt and thus for the
industrial production of borosilicate glass.

Composition: The borosilicate glass composition includes silicon dioxide (SiO2) in a

range from about 60% to 74% by total composition weight; boric oxide (B2O3) in a range
from about 9% to 25% by total composition weight; aluminium oxide (Al2O3) in a range
from about 7% to 17% by total composition weight; and at least one alkali oxide in a range
from about 2% to 7% by total composition weight.

Uses: Kitchen wares, Chemical Plants, Electrical insulators, Superior Laboratory

apparatus, Industrial pipeline for corrosive liquids, Gauge glass etc.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
3. Lead GLASS or Flint Glass

 It is made up of lead oxide fluxed with silica and K2CO3

 Its approximate composition is [Link]. SiO2

Lead glass has a lower softening temperature than soda glass and higher refractive index and
good electrical properties. It is bright lustrous and possesses high specific gravity.

Composition: Lead glass contains typically 18–40% (by weight) lead (II) oxide (PbO), while
modern lead crystal, historically also known as flint glass due to the original silica source,
contains a minimum of 24% PbO. Lead glass is often desirable for a variety of uses due to its
clarity.

Uses: High-quality table wares, optical lenses, Neon sign tubing, Cathode ray tubes, Electrical
insulators, Crystal art objects or cut glass, Windows and Shields for protection against X-rays
and Gamma rays in medical and atomic energy fields etc.

4. Aluminosilicate Glass

 This type of glass possesses exceptionally high softening temperature.

 Aluminosilicate glass is one of the most rare glass, some of these types
have been used in space shuttle windows, gauges and thermometers.
Composition: This mineral-based material contains 57-60% silicon dioxide (SiO2) and 16-
20% aluminium dioxide (Al2O3), along with small amounts of 5-7% lime (CaO), 6-12%
magnesium oxide (MgO), boron trioxide (B2O3), among other cations.

Uses: It is used for high-pressure mercury discharge tubes, chemical combustion tubes etc.

5. Toughened Glass

It is a type of safety glass processed by controlled thermal or chemical treatments to increase

its strength compared with normal glass.
Tempering puts the outer surfaces into compression and the interior into tension. Toughened
glass is a material that is extremely flexible and versatile which means that we can use it as per
our needs and requirements.

Composition: Toughened glass or tempered glass is glass that has undergone processes of
controlled thermal treatment to increase its strength. It is four times stronger than normal
annealed glass. Toughened glass is made from annealed glass that has been heated to
approximately 650 ⁰C and then rapidly cooled.

Uses: For making window shields for fast-moving vehicles, Windows of furnaces and
automatic opening doors.

6. Potash lime or Hard Glass

 Potash lime glass is made with silica (sand), Calcium Carbonate and Potassium
carbonate.
 The approximate composition is K CO .CaO.6SiO .
2 3 2
 They possess a high melting point.
Uses:- These glasses are costlier than soda-lime glass and are used for chemical apparatus,
combustion tubes and glassware which are used for heating operations.

7. Wired Glass

Wired glass does not fall apart into splinters when it breaks and is fire-resistant. It is made by
fusing wire in between the two glass layers. Page | 8

Uses:- For making fire-resistant doors, roofs, skylights and windows.

8. Coloured Glass

These are produced by the addition of metallic oxides to soda lime silica glass. Chromium
oxide produces a green colour, Cobalt produces a blue colour, Iron produces a greenish blue
colour, & Gold, Copper, Selenium, and Colloidal particles produce a red colour.

Uses:- Used for window panels, fancy articles, decorative tiles etc.

9. Laminated Glass

It is a type of safety glass that holds together when shattered. In the event of breaking
it is held in place by an interlayer typically of polyvinyl butyral, ethylene-vinyl.

Uses: Car windshields, glass railings, skylights, roofs, glass floors etc.

MANUFACTURE OF GLASS

Raw Materials Classification

1. Network Formers (NWF): These are the oxides of elements, which are surrounded by
four oxygen atoms in the tetrahedral chain forming a highly cross-linked network of
chemical bonds. Typical examples: Sand or quartz (SiO ), B O , GeO , P O
2 2 3 2 2
2. Network Modifiers (NWM): These are the large diameter elements having high
coordination numbers.
They alter the network structure.
They are usually present as ions, bonded to non-bridging oxygen atoms.
Examples: Oxides of alkali metals, Na O, K O
2 2
Oxides of alkaline earth metals, CaO, MgO, Al O
2 3
Oxides of lead,
Oxides of zinc

3. Oxidising Agents: Materials like NaNO3 or certain peroxides are used to reduce the
colour of impurities like iron oxide and magnesium oxide

4. Refining Agents: Salt cake (Na SO ) is used to remove impurities in the form of scum.
2 4
To reduce or eliminate the quantity of air bubbles from the molten glass, refining agents
like As O and small amounts of feldspar are added to the glass.
2 3
5. Collets: Waste or broken glass pieces are called cullets. Cullets lower the cost of
production and help in the fusion of glass batches.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
6. Colouring Agents: During the manufacture of coloured glass, some metal oxides are
used as colouring agents. For example, Oxides of chromium and iron give green glass.
Oxides of Manganese give a violet glass
Oxides of Ce and Ti give yellow glass.

Glass Manufacturing Process

The manufacture of glass is a complex process that involves several steps, from raw material
preparation to the final product. Glass manufacturing can be broadly divided into four main
stages: batch preparation, melting, forming, and finishing. The manufacture of glass involves
several key stages, including batch preparation, melting, forming, and finishing. Each stage
requires precise control to produce high-quality glass products with the desired properties.
Advances in technology and environmental controls continue to improve the efficiency and
sustainability of glass manufacturing:

1. Preparation of glass batch and melting of glass batch.

2. Fabrication of articles
3. Annealing of articles formed
4. Finishing treatment

1. Batch Preparation

The first step in glass manufacturing is preparing the batch, which consists of raw materials
mixed in specific proportions. The primary raw materials include:

 Silica (SiO2): The main component of glass, usually sourced from sand.
 Soda (Na2O): Lowers the melting temperature of silica, typically sourced from soda
ash (sodium carbonate, Na2CO3).
 Lime (CaO): Improves the chemical durability and hardness of glass, sourced from
limestone (calcium carbonate, CaCO3).
 Other Additives: Depending on the type of glass being produced, various additives
may be included to impart specific properties, such as colourants (iron oxide for green,
cobalt for blue), alumina (Al2O3) for increased durability, and magnesium oxide (MgO)
to improve chemical resistance.

The raw materials are carefully weighed and mixed to form a homogeneous batch.

Glass batch calculations involve determining the proportions of raw materials needed to
produce a specific glass composition. Here is a step-by-step guide:

Step-by-Step Guide

1. Determine the Desired Composition:

o Define the glass composition you want, usually in terms of oxides (e.g., SiO₂,
Na₂O, CaO) and their respective percentages.
2. List Raw Materials:
o List the raw materials available for the batch (e.g., silica sand, soda ash,
limestone) and their compositions, particularly the oxides they provide.
3. Calculate the Contribution of Each Raw Material:
o Determine the amount of each oxide contributed by each raw material.
4. Set Up Equations:
o Set up a system of linear equations based on the desired oxide composition and
the contributions from each raw material.
 5. Solve the Equations:
o Solve the system of equations to find the proportion of each raw material
needed to achieve the desired glass composition.

Example Calculation

Example 1 Page | 10
You are to produce a glass with the following composition by weight: SiO₂: 70%; Na₂O: 15%;
CaO: 10%; Others: 5%. If the raw materials are Silica sand (contains 100% SiO₂), Soda ash
(contains 58% Na₂O), Limestone (contains 56% CaO). Determine the glass batch calculation.

To calculate the glass batch for producing a glass with the given composition, we'll follow a
systematic approach. The desired glass composition is:

 SiO₂: 70%
 Na₂O: 15%
 CaO: 10%
 Others: 5%

Given raw materials are:

 Silica sand (contains 100% SiO₂)

 Soda ash (contains 58% Na₂O)
 Limestone (contains 56% CaO)

We'll calculate the amount of each raw material required to achieve the desired glass
composition.

1. Determine the Mass of Each Component in the Glass

Assume we want to produce 100 kg of glass.

 SiO₂: 70%×100 kg=70 kg

 Na₂O: 15%×100 kg=15 kg
 CaO: 10%×100 kg=10 kg
 Others: 5%×100 kg=5 kg

2. Calculate the Required Amount of Each Raw Material

a. Silica Sand (100% SiO₂)

To provide 70 kg of SiO₂:

70 𝑘𝑔 𝑜𝑓 𝑆𝑖𝑂2
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑆𝑖𝑙𝑖𝑐𝑎 𝑆𝑎𝑛𝑑 = = 70 𝑘𝑔
1.00

b. Soda Ash (58% Na₂O)

To provide 15 kg of Na₂O:
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES

15 𝑘𝑔 𝑜𝑓 𝑁𝑎2 𝑂
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑆𝑜𝑑𝑎 𝐴𝑠ℎ = ≈ 25.86 𝑘𝑔
0.58

c. Limestone (56% CaO)

To provide 10 kg of CaO:

10 𝑘𝑔 𝑜𝑓 𝐶𝑎𝑂
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐿𝑖𝑚𝑒𝑠𝑡𝑜𝑛𝑒 = ≈ 17.86 𝑘𝑔
0.56

3. Result

To produce 100 kg of glass with the desired composition, you need:

 Silica Sand: 70 kg
 Soda Ash: 25.86 kg
 Limestone: 17.86 kg
 Others: 5 kg (this would include any other materials needed)

These are the amounts of raw materials required to achieve the desired glass composition.

Example 2

Glass composition: 65CaO-35Al2O3

Molecular weights of components (in g mol-1):
CaO = 56.08 Al2O3 = 101.96
-1
Molecular wt of glass: (0.65 x 56.08) + (0.35 x 101.96) = 72.14 g mol
The weight fraction of each component:
CaO = (0.65 x 56.08) / 72.14 = 0.505
Al2O3 = (0.35 x 101.96) / 72.14 = 0.495
For 100 grams of glass: CaO = 0.505 x 100 = 50.5 g
Al2O3 = 0.495 x 100 = 49.5 g

Example 3

Glass composition: 20Na2O-80SiO2

-1
Molecular weights of components (in g mol ):
Na2O = 61.98 SiO2 = 60.09
-1
Molecular wt of glass: (0.20 x 61.98) + (0.80 x 60.09) = 60.47 g mol
The weight fraction of each component:
Na2O = (0.20 x 61.98) / 60.47 = 0.205
SiO2 = (0.80 x 60.09) / 60.47 = 0.795
For 100 grams of glass: Na2O = 0.205 x 100 = 20.5 g
SiO2 = 0.795 x 100 = 79.5 g
Sodium oxide is not stable in air, so we must use a batch component such as Na2CO3, which
yields Na2O after decomposition. It is necessary to multiply the desired quantity of Na2O by
the gravimetric factor for Na2CO3 (1.71), to obtain the weight of Na2CO3 (35.05 g) to be used
to yield the desired 20.5 g of Na2O
Example 4

Glass composition: 20Na2O-5Al2O3-75SiO2

-1
Molecular weights of components (in g mol ):
Na2O = 61.98 Al2O3 = 101.96 SiO2 = 60.09
-1
Molecular wt of glass: (0.20 x 61.98) + (0.05 x 101.96) + (0.75 x 60.09) = 62.56 g mol Page | 12
The weight fraction of each component:
Na2O = (0.20 x 61.98) / 62.56 = 0.198
Al2O3 = (0.05 x 101.96) / 62.56 = 0.0815
SiO2 = (0.75 x 60.09) / 62.56 = 0.720
For 100 grams of glass: Na2O = 0.198 x 100 = 19.8g
Al2O3 = 0.0815 x 100 = 8.15 g
SiO2 = 0.720 x 100 = 72.0 g

Small compositional changes are often excluded from batch calculations.

For example, it is common to use a base glass of fixed composition to study the effects of minor
additions of other components.
These additions are usually expressed as wt % additions. One might, for example, consider the
effect of arsenic oxide as a fining agent by preparing the same batch containing 0, 0.1, 0.2, or
0.5 wt % additions of As O to a base soda-lime-silicate glass composition.
2 5
In reality, the actual molar composition of the glass changes as the arsenic oxide content
changes.

Adjusting for Practicality

In practice, you might iterate the calculations or adjust the raw materials until a feasible
batch composition is found. You may also use specialized software or spreadsheets for more
complex calculations.

2. Melting

The mixed batch is then fed into a furnace where it is melted at high temperatures (typically
between 1400°C to 1600°C). The furnace can be of different types, including:

 Pot Furnace: Used for small-scale or speciality glass production.

 Tank Furnace: Continuous furnaces used for large-scale production.
o Release of Gases
 Initial heating of a glass-forming batch usually results in the release of
some moisture, which may have been absorbed on the particles, or
combined as water of hydration or as hydroxyl.
 Many of the components of common glass-forming batches are somewhat
hygroscopic, readily absorbing some water from the surroundings.
 Boric oxide may partially convert to boric acid (H3BO3), CaO may form
Ca(OH)2, etc.
 Other components already contain water, e.g., NaOH, clays, hydrated
alumina, NaB4O7.lOH2O, which will be released at moderate
temperatures.
 The temperature at which this water is released will depend upon
the nature of its bonding to the materials, i.e., physical or chemical, and
the strength of these bonds.
 Removal of this water carries heat from the batch and increases the cost
of processing.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Far more gas is released during the decomposition of carbonates,
sulphates, and nitrates.
 The gases released expand to volumes much greater than that of the
starting batch, resulting in considerable mixing and stirring action, which
aids in the homogenization of the melt.
 The creation of so much gas, however, also leads to the formation of an
extremely large number of bubbles, which must be removed from the melt
before processing is completed.
o Formation of liquid phases
 Liquid phases are formed by the direct melting of batch components, by
melting of decomposition products, and by melting of eutectic mixtures
formed from the batch components.
 In soda-lime-silicate batches, we find eutectic mixtures of sodium and
calcium carbonates, which melt at 775 oC, and sodium disilicate and silica,
which melt at about 800 oC.
 At this point, the liquid phases are very fluid, the release of gases occurs
rapidly, and the mixture of liquid and solids is very turbulent. As the
temperature increases, the rates of dissolution of the refractory particles
such as sand, alumina, and feldspars increase.
 The increase in concentration of these components causes a rapid increase
in viscosity, and the release of additional gases as the solubility of CO, and
other gases decreases with increasing silica concentration in the melt.
 Since the viscosity increases rapidly as the silica content of the liquid
increases, the temperature must be increased even further to keep the melt
fluid enough for thorough mixing between liquid and remaining solids.
 The final stage of the melting process, in which the remaining silica and
other refractory components are completely dissolved and the melt
becomes homogeneous, occurs much more slowly due to the high viscosity
of the melt.
 The time required to completely dissolve the original batch is known as
the batch-free time.
 Although the definition of batch-free time is straightforward,
determination of the exact time at which the last remaining trace of batch
remains in the melt is difficult.
 In general, the determination of the batch-free time is subject to a variety
of errors, including prejudice on the part of the researcher.
 Other factors include overall glass composition, specific batch
components used to obtain that composition, batch homogeneity, grain
size of batch components, and the grain size and amount of cullet added
to the batch.
 The use of cullet, or scrap glass, not only reduces waste but also aids in
reducing the batch-free time by both reducing the amount of refractory
material in the batch and by providing additional liquid throughout the
melting process.
 The overall glass composition is by far the most important factor in
controlling the batch-free time.
 Simple oxide mixtures, such as those used to produce calcium aluminate
glasses, often form eutectic mixtures which melt directly with very short
batch-free times.
 Many non-silicate melts are very fluid at any temperature above the
melting point of their components and rapidly dissolve all batch particles.
 Borate, phosphate, and germanate melts can be formed at much lower
temperatures than are typically required for silicate melts.
  As a result, it is usually easier to decrease their viscosity by increases in
temperature, e.g., an increase in temperature from 1000 to 1200 oC is
more easily attained than an increase from 1400 to 1600 oC
 The choice of batch components is also important in controlling batch-free
time. Many batch components can be supplied from a variety of raw
materials.
 Batch segregation inhibits melting by separating components, which Page | 14
might otherwise form eutectic mixtures (the specific composition of at
least two solid components that produce a change of phase to liquid at a
certain temperature).
 Time invested in the initial mixing of batch components is usually repaid
in improved glass quality and reduced requirements for melting
temperature and time.
 Changes in particle size can seriously affect the batch-free time for melts.
 While fine particles melt more rapidly, they can also agglomerate to form
larger, porous particles, which effectively prevent penetration of the
viscous liquid to the particle surfaces. Since these agglomerations have a
low bulk density, they can float to the surface of the melt, which
significantly slows the dissolution process.
 The escape of gases is inhibited when very fine particles are used since
the channels between the particles are reduced in size.
 The use of very fine particles can result in the blockage of these channels
in the early stages of the melting process, which can suppress
decomposition reactions.
o Melting Accelerants
 The most important methods for accelerating the melting process are
based on changes in batch raw materials.
 Replacement of a small portion of sodium carbonate by sodium sulphate,
for example, speeds the dissolution of sand by forming additional, lower
melting eutectic mixtures.
 As more silica dissolves into the melt, sulphates separate from the melt in
the silica-rich regions surrounding the silica particles.
 These sulphates decompose as the temperature increases, reacting with
the silica particles to release sodium and form sodium metasilicate, which
melts readily to form a fluid liquid.
 The release of SO3 creates a vigorous stirring effect which aids in
homogenization of the melt and improves the contact between silica
particles and the surrounding liquid.
 Other melting accelerants are also based on the replacement of some of
the sodium carbonate by more easily melted compounds such as NaOH,
NaF, or NaCl, all of which form very fluid liquids upon melting.
 When melts are formed under an atmosphere containing oxygen, halides
will gradually exchange with the oxygen in the surrounding atmosphere,
the melt composition will revert to the desired oxide composition, and the
viscosity will increase.
 Since the batch has dissolved by this time, however, the use of the halide
will still result in a shorter batch-free time.
 Components which force water to enter the melt are especially effective in
accelerating melting processes. Water is very efficient in reducing the
viscosity of oxide melts.
 The source of the water is unimportant, so long as it is in direct contact
with the liquid.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 Water can be provided by the use of components such as H3BO3 instead of
B2O3, or NaOH instead of Na2CO3, by wetting the initial batch, or by
changes in the furnace atmosphere, which increase the partial pressure of
water vapour in the combustion gases.
 Changes from gas-air combustion to gas-oxygen combustion result in
higher water vapour contents in furnace atmospheres, which may lead to
reductions in overall melting times.
 Mechanical methods which improve contact between batch particles may
also accelerate melting processes.
 Compaction of raw materials into either dry or moist bricks, pellets, or
granules increases the melting rate by improving heat transfer to the
individual particles, and by providing better contact between components
which will react to form eutectic melts.
o Volatilization of Components from Melts
 A large number of the components of glasses are quite volatile at elevated
temperatures.
 Loss of these components can significantly alter the composition of the
glass obtained after prolonged melting, as compared to that obtained for
short melting times.
 Volatilization losses are particularly significant for alkali oxides, lead,
boron, phosphorus, halides, and other components which have high
vapour pressures at high temperatures.
 The rate of loss of alkali increases rapidly in the order of Li < Na < K < Rb
< Cs.
 The loss of a component can be reduced by increasing the concentration
of that component in the atmosphere above the melt.
 Covering the melt will force the partial pressure of the volatile components
to increase directly above the melt, establishing a dynamic equilibrium
between the dissolved and vaporized species, and preventing significant
loss of those components.
 These losses can usually be reduced dramatically by lowering the melt
temperature.
 Covering the melt is usually not possible in large commercial melting
tanks.
 It may be necessary to allow for losses by providing excess concentrations
of components known to vaporize from a given melt.
 This procedure is quite efficient for continuous melting of a constant
composition, where analysis of the product over some time can be used to
establish the exact amount of excess component needed to counter the
volatilization losses.
 In a few cases, it may be possible to add a component to the furnace
atmosphere to prevent its loss from the melt.
 This procedure can be used to aid in retaining halides or water in melts
but is of little use for cations.
 While control of volatilization losses is a well-recognized problem in the
production of commercial glasses, it is often totally overlooked in
laboratory studies.
 A simple weight loss method can be used to determine if the yield of glass
is equal to that predicted in the batch calculation.
 If the yield differs from the expected value by more than a few tenths of a
per cent, the sample composition is certainly suspect.
  Experience has shown that the production of a soda-lime-silicate glass
using Na2CO3, CaO, and SiO2 will result in a loss of about 0.1 wt % relative
to the expected yield.
 This loss is usually due to adsorbed water vapour on the batch materials
and not to detectable loss of sodium.
 This loss can be contrasted with values of 10 to 20 wt % occasionally
observed for melts containing rubidium, caesium, thallium, and other Page | 16
highly volatile, high atomic weight species.
 While this method does not reveal the identity of the species lost, it
certainly alerts the researcher to the possibility of serious error in the
sample composition.
o Fining or Refining of Glass Melts
 The terms fining and refining refer to the removal of gaseous inclusions,
or bubbles, from the melt.
 Although the presence of bubbles in a glass sample is not necessarily
detrimental for many scientific studies, bubbles are undesirable in most
commercial glasses.
 Bubbles in commercial products are almost always considered flaws and
result in the rejection of the product.
 These gas-filled inclusions may occur as very small spheres (< 0.4 mm
diameter), which are frequently called seeds and are often found in
clusters, or as larger, isolated spheres, more commonly referred to as
bubbles.
 The fining of a melt begins during the melting process but typically
extends to times well after the complete disappearance of a residual batch.
o Sources of Bubbles in the Glass Melts
 Bubbles can be formed by the physical trapping of atmospheric gases
during the initial phase of batch melting, or by the decomposition of batch
components.
 The gases in the interstices between batch particles may be trapped as the
particles begin to soften and form a viscous liquid.
 As the viscosity decreases with increasing temperature, these interstices
become fully surrounded by liquid. Surface forces then cause these
interstices to assume the spherical shape of bubbles.
 These bubbles contain gases characteristic of the melting atmosphere,
which may be air, combustion gases, or some gas deliberately introduced
to control chemical reactions with the batch.
 Prevention of the formation of these bubbles involves the elimination of
gas from the interstices of the batch, i.e., melting under vacuum.
 Trapping of atmospheric gases is enhanced by the use of very fine sand in
the batch, or by the use of batch components of widely differing particle
sizes.
 Both factors create a large concentration of very fine interstices within the
unmelted batch. Agglomeration of particles is particularly effective in
trapping atmospheric gases within the agglomerate, which is effectively
surrounded by the viscous melt.
 Mechanical stirring of a melt can introduce bubbles by trapping air and
forcing it into the melt.
 Decomposition of batch materials can produce extremely large quantities
of gases such as CO2, SO3, NOx, H2O,etc.
 Reactions with metals in contact with the melt can generate oxygen,
carbon dioxide, or hydrogen by electrolytic reactions.
ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 Corrosion of refractories can open previously closed pores to the melt,
releasing the gas contained in those pores into the melt.
 Residual carbon in refractories, or carbide refractories such as Sic, can
react with oxide melts to form CO2 or CO.
 The products of all of these reactions can agglomerate to form bubbles.
 Bubbles can also be formed by precipitation from the melt whenever
supersaturation occurs for a specific gas.
 Since many gases have a large enthalpy of solution in glass-forming melts,
their solubility in these melts is a strong function of temperature.
 Species which alter their chemical form with temperature or changes in
melt composition are particularly susceptible to precipitation from melts
where they were previously soluble.
 Carbon dioxide, for example, is present in silica-rich melts as CO2
molecules, whereas it chemically reacts with alkali-rich melts to form
carbonate species, which are far more soluble than the molecular species.
 The solubility of carbon dioxide in the alkali-rich regions surrounding
silica grains during the early stages of batch melting is quite high.
 As the silica grains dissolve, the melt becomes locally enriched in silica,
which converts the dissolved species to CO2 molecules, which have a much
lower solubility.
 The melt thus becomes supersaturated locally and CO2 bubbles form.
 As a result, CO2 bubble generation will continue long after the initial
decomposition of the carbonate batch components.
 Sulphur solubility is very sensitive to the oxidation state of melts.
 Under reducing conditions, sulphur dissolves as sulphide ions, while
oxidizing conditions produce sulphate ions.
 Reduction of the oxygen partial pressure over an oxidized melt will shift
the equilibrium between sulphide and sulphate states, with a reduction in
overall sulphur solubility.
 A previously under-saturated melt will now become supersaturated and
bubbles will form.
 Changes in melt chemistry will alter sulphur solubility just as they alter
carbon dioxide solubility, with similar results.
 Melt temperature is also very important, since sulphate solubility
decreases with increasing temperature, while sulphide solubility increases
with increasing temperature.
 Temperature changes can thus alter the degree of solubility of sulphur in
melts in opposite directions for oxidized and reduced melts.
 Oxygen can also be released into melts by changes in the oxidation state of
the surrounding atmosphere.
 Changes in the oxidation state of polyvalent ions such as iron, chromium,
manganese, etc. can alter the state of oxygen from chemically bound to
physically dissolved molecules, as in the reaction:
4Fe3++ 2O2-→ 4Fe2++ O2(g)
 Since the solubility of molecular oxygen is much less than that of
chemically bound oxygen, super-saturation occurs and oxygen bubbles
form during the reduction of polyvalent species.
 Reboil, or the formation of bubbles in previously bubble-free glasses, is a
special case of the precipitation phenomena discussed above.
 Reboil specifically refers to bubble formation from bubble-free materials
during reheating of glasses from the solid state, or increases in melt
temperature.
  Gases which increase in solubility with increasing temperature do not
contribute to reboil, since super-saturation occurs because the solubility
of the dissolved gas is less at the higher temperature.
 Reboil is especially common for SO3, where the solubility in commercial
soda-lime-silicate melts decreases by 3 orders of magnitude on heating
from 1100 to 1400 oC.
 Under these conditions, a small increase in temperature can convert a Page | 18
previously under-saturated melt into a highly super-saturated one, with
the consequent formation of many bubbles.
 Sulphur-induced reboil can also occur if previously oxidized melts
containing sulphates are placed in contact with previously reduced melts
containing sulphides.
 The change in melt chemistry at the interface can result in a
supersaturated solution due to the differing solubility of the two forms of
dissolved sulphur.
o Fining Agents
 Chemical methods for the removal of bubbles from melts depend upon the
addition of batch components collectively termed fining agents.
 Fining agents release large quantities of gases, which form large bubbles
which rapidly rise to the surface of the melt.
 These large bubbles tend to carry smaller bubbles and seeds to the surface
as well.
 In addition, some fining agents cause the absorption of O2 from bubbles
at lower temperatures, thus reducing the size of the seed due to diffusion
from the bubble into the melt.
 The seed eventually shrinks to below the critical radius, where the surface
energy causes the complete disappearance of the bubble.
 Arsenic and antimony oxides are the most efficient and thoroughly studied
chemical fining agents.
 Arsenic and antimony oxides are usually added to the batch in 0.1 to 1 wt
% quantities as trioxides, but pentoxides, arsenates, antimonates, and
arsenic acid are also used under special circumstances.
 Alkali and alkaline earth oxides in the melt allow the formation of
arsenates, which are less volatile than the trioxides.
 The absence of these basic oxides can seriously compromise the efficiency
of arsenic and antimony oxides as fining agents, due to the rapid loss of
the fining agent through volatilization.
 The fining action of arsenic and antimony oxides results from a series of
chemical reactions which occur at different stages of the melting process.
 Although controversial, one possible sequence of events might be
described as follows.
 During batch melting, these oxides react with nitrates to release nitrogen
oxides and O2, as, for example, in the reaction:
4KNO3 + 2As2O3 → 2K2O+ 2As2O3 + 4NO(g) + O2(g)
Analogous reactions occur for Sb2O3 and other nitrates.
 These reactions release copious quantities of NO and O 2, which form large
bubbles which rapidly rise to the surface.
 These bubbles stir the batch and sweep smaller bubbles to the surface.
 After batch decomposition is completed, melts are usually heated to higher
temperatures and held until completely fined.
 Since the trioxide is more stable than the pentoxide at these
temperatures, the pentoxide produced via reaction with nitrates
decomposes via the reaction:
ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
As2O5 → As2O3 + O2 (g)
for arsenic, and the analogous reaction for antimony.
 These reactions produce O2 bubbles, which can either form new bubbles
or diffuse into nearby smaller bubbles, thus increasing their size and rise
rate.
 Any bubbles remaining in the melt at this point will be highly enriched in
oxygen relative to the bubbles previously present.
 Lowering the temperature will result in a shift toward the pentoxide,
which requires absorption of oxygen from the melt.
 As the dissolved oxygen is consumed, oxygen from nearby bubbles will
diffuse into the melt, reducing their internal pressure and hence reducing
their diameter.
 Once the diameter is reduced to a very small value (< 0.1 mm), the surface
energy will become sufficient to cause contraction of the bubble and a rise
in internal pressure, P, as described by the expression:
2𝑦
𝑃=
𝑟
where y is the surface energy and r is the bubble radius.
 The high internal pressure will cause accelerated diffusion from the bubble
into the melt until the bubble is completely consumed.
 Although other fining agents are usually less efficient, the toxicity of
arsenic and antimony oxides often forces the use of other approaches to
chemical fining.
 Sodium sulphate, for example, also serves as a source of considerable gas
during batch decomposition, as well as providing a portion of the sodium
for soda-lime-silicate melts.
 The extreme temperature and compositional sensitivity of sulphur
solubility in melts play an important role in the fining process.
 Sulphates readily dissolve into the alkali-rich regions of melts during
batch decomposition.
 As the silica dissolves into these alkali-rich regions, the solubility of
sulphates decreases, releasing gas into the melt, as described by the
reaction:
Na2SO4 + nSiO2 → Na2O-nSiO2 + SO3 (g)
 The SO3 immediately decomposes into O2 and SO2 via the reaction:
2SO3 → 2SO2 (g) + O2 (g)
 The SO2 molecules diffuse into nearby bubbles, while the O2 either diffuses
into bubbles or dissolves into the melt. These bubbles then rise to the melt
surface.
 Lowering the temperature can result in the reabsorption of SO2 from
bubbles to form sulphate chemically dissolved in the melt, which will
cause the bubbles to shrink and disappear like that described for arsenic
and antimony fining.
 Sulphate fining is strongly affected by the reactions with furnace gases or
other sources of carbon.
 Reactions between SO3 and either C or CO produce SO2 and CO2, releasing
large quantities of gas.
 Since carbon serves as both a reactant to produce CO2 and as a reducing
agent, which alters the solubility of sulphides and sulphates in melts, the
chemistry of sulphate-carbon fining is very dependent upon the overall
melt composition, temperature, and surrounding atmosphere.
 Nitrates can also act as fining agents even in the absence of arsenic or
antimony oxides.
 Decomposition of nitrates releases large quantities of nitrogen and
oxygen, which form large bubbles.
 The low decomposition temperatures (500 to 800 oC) of alkali nitrates,
however, limit their usefulness as fining agents, since most of the gas
release occurs before the melt forms.
 Halides are most useful as fining agents through their efficiency in
lowering the viscosity of melts. Page | 20
 Since exposure of melts containing halides to oxygen atmospheres will
result in a gradual replacement of the halide by oxygen, the viscosity will
gradually rise.
 Since most of the bubbles will have already risen to the surface, this
delayed viscosity increase may not necessarily be detrimental to the fining
effect of halides.
 Halides are particularly effective in fining of high alumina content melts.
 Oxides of a few polyvalent cations can be used as fining agents by acting
as sources of O2, like arsenic and antimony oxides.
 Cerium oxide, for example, can be reduced to release oxygen via the
reaction:
4CeO2 → 2Ce2O3 + O2
 Since cerium oxide is often added in small quantities to commercial glass-
forming melts for other purposes, e.g., prevention of solarization, the
fining effect can be considered a beneficial side effect.
 Other oxides of polyvalent cations (MnO2, Fe2O3, Pb3O4, etc.), which are
added for reasons other than their fining action, can also act as minor
fining agents via similar reactions.
o Homogenizing of Glass Melts
 The fluid produced during the initial batch decomposition process is very
heterogeneous.
 This heterogeneity is gradually reduced by the stirring action of rising
bubbles during the fining process.
 Production of an acceptably homogeneous glass, however, usually
requires additional time for diffusion processes to improve the
homogeneity of the melt.
 Homogeneity is normally described in a negative sense: a homogeneous
melt is free from significant heterogeneities.
 The definition of a “significant” heterogeneity is often difficult and varies
dramatically with the intended end use of the glass.
 A perfectly acceptable level of homogeneity for window glass might be
completely unacceptable for glass used as an optical lens.
 Gross defects such as bubbles, seeds, and stones (particles of undissolved
material), are often clearly visible and result in the rejection of most
commercial glasses.
 The terms striae and cord are used to describe variations in local
composition within a glass.
 Striae are two-dimensional regions, or layers, of a composition different
from the bulk, while cords are similar regions which are effectively one-
dimensional veins in the glass.
 These regions are most often detected by visual observation, where a
“wavy” appearance is caused by local refractive index variations.
 In coloured glasses, regions of inhomogeneity can often be detected by
variations in colour intensity.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 The extent of these regions is designated as the scale of the inhomogeneity,
while the degree of departure from the bulk composition, or property, is
designated as the intensity of inhomogeneity.
 Quantitative description of the degree of inhomogeneity of a glass is
difficult.
 Density or refractive index measurement on crushed glasses can be used
as a relative measurement of the intensity of inhomogeneity.
 Visual examination of a pattern consisting of dark, parallel lines through
a glass plate is frequently used as a method for the detection of optical
distortions due to cord and striae.
 Since the pattern resembles the coat of a zebra, this technique is called the
zebra board method.
 Poor homogeneity frequently results from poor mixing of the original
batch materials.
 The effect of mixing is especially important for laboratory melts, which are
usually not stirred and are held at melt temperatures for times which are
much less than those used for commercial glass production.
 Striae and cord can be formed by reactions with refractories, and at the
melt-atmosphere boundary due to volatilization of batch components,
especially alkali, boron, or lead.
 Decreasing the grain size of the batch improves homogeneity by reducing
the scale of the inhomogeneity of the initial melt.
 Stirring by mechanical stirrers, the creation of convection flow in the melt,
or the bubbling of a gas through a melt can improve homogeneity.

During melting, the raw materials react to form a molten glass. The key reactions include:

CaCO3 → CaO + CO2

Na2CO3 → Na2O + CO2
SiO2 + Na2O + CaO → Na2O⋅CaO⋅6SiO2

The melting process aims to produce a homogeneous, bubble-free, and impurity-free molten
glass.

Questions
1. Define the role of each of the following in a glass batch. Give at least 2 examples
of each:
(a) Glass-forming oxide
(b) Modifier oxide (flux)
(c) Property modifier oxide
(d) Colorant
(e) Fining agent

2. Calculate the batch weights of each component needed to yield 50 grams of

glass for each of the following compositions. The raw materials to be used are
SiO2, Na2CO3, CaO, Al2O3, PbO, PbF2, and H3BO3. Indicate the total batch
weight, the molecular weight of the glass, and the weight of each component for
each case:
(a) Na2O-2SiO2
(b) 15 Na2O-10 CaO-75 SiO2
(c) 2Na2O-A12O3-6SiO2
(d) 20 PbO-80 B2O3
(e) 20 PbF2-80 B2O3
 3. Convert the following glass compositions from wt% to mol%, or vice versa:
(a) 25 mol % K2O-75 mol % SiO2,
(b) 25 wt % K2O-75 wt % SiO2
(c) 20 mol % Na2O-80 mol % SiO2
(d) 12 soda-9 lime-3 magnesia-2 alumina-74 silica (all given in wt %)
(e) 20 PbO-80 B2O3 (mol %)
Page | 22
3. Forming

Once the molten glass is ready, it is formed into various shapes and products. Different forming
methods are used depending on the desired product:

 Float Glass Process: Used for producing flat glass for windows and mirrors. Molten
glass is floated on a bed of molten tin, creating a flat, smooth surface.
 Blow and Blow Method: Used for making bottles and other hollow containers.
Molten glass is first blown into a parison (preliminary shape) and then blown again into
the final shape using a mould.
 Press and Blow Method: Similar to the blow and blow method but uses a plunger to
press the glass into the parison mould before blowing it into the final shape.
 Drawing: Used for producing glass fibres and sheets. Molten glass is drawn through
dies to form thin strands or sheets.
 Casting: Used for making glass blocks and lenses. Molten glass is poured into moulds
and allowed to solidify

4. Finishing

After forming, the glass products undergo various finishing processes to achieve the desired
properties and quality:

 Annealing: Slowly cooling the glass to relieve internal stresses and prevent cracking or
shattering. This is typically done in an annealing lehr.
 Cutting and Grinding: Cutting glass to size and grinding edges to remove sharpness.
 Polishing: Polishing surfaces for clarity and smoothness, particularly for optical glass
and mirrors.
 Tempering: Heating the glass and then rapidly cooling it to increase its strength.
Tempered glass is used for safety applications.
 Coating: Applying coatings to impart specific properties, such as reflective coatings for
mirrors or anti-glare coatings for screens.
 Decorating: Adding decorative elements through processes like etching, painting, or
screen-printing.

Quality Control Measures

Throughout the manufacturing process, rigorous quality control measures are employed to
ensure the glass meets specified standards. This includes checking for:

 Homogeneity: Ensuring the glass is free from bubbles, inclusions, and striations.
 Strength and Durability: Testing mechanical properties like strength and
resistance to thermal shock.
 Optical Properties: Measuring clarity, refractive index, and any colouration.
 Dimensional Accuracy: Ensuring the product meets size and shape specifications.

Environmental and Safety Considerations

 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Glass manufacturing can be energy-intensive and generate emissions. To address these
issues, manufacturers implement various measures:

 Energy Efficiency: Using advanced furnace technologies and heat recovery systems
to reduce energy consumption.
 Emission Control: Installing scrubbers, filters, and other pollution control devices
to minimize emissions of NOx, SOx, and particulate matter.
 Recycling: Incorporating recycled glass (cullet) into the batch to reduce raw material
consumption and energy usage.

SYNTHESIS GAS AND ITS UTILIZATION IN THE CHEMICAL INDUSTRY

Synthesis gas, sometimes known as syngas, is a useful intermediary in the chemical sector. The
main ingredients of the mixture are hydrogen (H₂) and carbon monoxide (CO), with different
concentrations of methane (CH₄), carbon dioxide (CO₂), and other contaminants. Natural gas,
coal, biomass, and even waste materials can all be used as feedstocks to create syngas using
procedures like gasification, partial oxidation, and steam reforming. In the chemical industry,
syngas is an essential intermediate that makes it possible to produce a large variety of chemicals
and fuels. Because of its adaptability and capacity to be made from a variety of feedstocks, it is
a crucial part of contemporary industrial chemistry. Syngas production and utilisation are
becoming more sustainable and efficient due to technological advancements and process
optimisation.

Production of Syngas

1. Steam Reforming:
o Feedstock: Natural gas (primarily methane).
o Process: Methane reacts with steam in the presence of a catalyst at high
temperatures (700-1000 °C).
o Reaction:

CH4 + H2O → CO + 3H2

o Additional Reaction (Water-Gas Shift Reaction):

CO + H2O → CO2 + H2

2. Partial Oxidation:
o Feedstock: Hydrocarbons (natural gas, oil residues).
o Process: Hydrocarbons react with a limited supply of oxygen.
o Reaction:

1
𝐶𝐻4 + 𝑂2 → 𝐶𝑂 + 2𝐻2
2

3. Gasification:
o Feedstock: Coal, biomass, or waste materials.
o Process: Feedstock reacts with oxygen and steam at high temperatures.
o Reaction:
C + H2O → CO + H2
C + O2 → CO2
CO2 + C → 2CO
Utilization of Syngas

Syngas is an important feedstock for many different chemical reactions, helping to produce
many necessary chemicals and fuels. The following are a few of the main uses:

1. Ammonia Production:
o Process: Haber-Bosch process. Page | 24
o Reaction: N2 + 3H2 → 2NH3
o Usage: Ammonia is used in fertilizers and explosives and as a precursor to many
nitrogen-containing compounds.
2. Methanol Production:
o Process: Methanol synthesis.
o Reaction:

CO + 2H2 → CH3OH

o Usage: Methanol is used as a fuel, solvent, antifreeze, and as a feedstock for

producing formaldehyde, acetic acid, and other chemicals.
3. Fischer-Tropsch Synthesis:
o Process: Converts syngas into liquid hydrocarbons.
o Reaction:

(2n+1)H2 + nCO → CnH2n+2 + nH2O

o Usage: Production of synthetic fuels (diesel, gasoline, and jet fuel) and
lubricants.
4. Hydrogen Production:
o Process: Water-gas shift reaction.
o Reaction:

CO + H2O → CO2 + H2

o Usage: Hydrogen is used in refining processes, ammonia production,

hydrogenation of fats and oils, and as a fuel in fuel cells.
5. Acetic Acid Production:
o Process: Carbonylation of methanol.
o Reaction:

CH3OH + CO → CH3COOH

o Usage: Acetic acid is used in the production of polymers (e.g., polyvinyl acetate),
as a solvent, and as a chemical reagent.
6. Synthetic Natural Gas (SNG):
o Process: Methanation of syngas.
o Reaction:

CO + 3H2 → CH4 + H2O

o Usage: SNG is used as a substitute for natural gas in energy applications.

 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Advantages of Syngas Utilization

 Feedstock Flexibility: Syngas can be produced from a variety of feedstocks, including

natural gas, coal, biomass, and waste, offering flexibility in raw material sourcing.
 Versatility: Syngas serves as an intermediate for producing a wide range of chemicals
and fuels, making it a cornerstone of the chemical industry.
 Environmental Benefits: When derived from biomass or waste, syngas can
contribute to reducing greenhouse gas emissions and utilizing waste materials
effectively.
 Energy Security: Domestic production of syngas from local resources can reduce
dependence on imported fuels and enhance energy security.

Challenges

 Capital and Operating Costs: The production of syngas, especially from coal or
biomass, can be capital-intensive and require significant operational costs.
 Carbon Dioxide Emissions: Depending on the feedstock and process, syngas
production can generate substantial CO2 emissions. Carbon capture and storage (CCS)
technologies are often required to mitigate this.
 Technical Complexity: The processes involved in syngas production and utilization
are technically complex and require advanced engineering and operational expertise.

Question: Discuss the production of liquid hydrocarbons using the Fischer-

Tropsch synthesis.

A chemical process known as the Fischer-Tropsch (FT) synthesis turns synthesis gas—a
mixture of hydrogen and carbon monoxide—into liquid hydrocarbons. In addition to waxes
and lubricants, this process can yield a broad variety of hydrocarbons, including fuels like jet
fuel, diesel, and petrol. Franz Fischer and Hans Tropsch invented the FT synthesis at the
beginning of the 20th century. A flexible method for turning synthesis gas into liquid
hydrocarbons, such as fuels and specialised chemicals, is the Fischer-Tropsch synthesis. It is a
crucial technology for the chemical and energy sectors because of its capacity to use a variety
of feedstocks and generate high-quality outputs. To maximise the process's sustainability and
deployment, nevertheless, its financial and environmental issues need to be resolved.

Overview of the Fischer-Tropsch Process

The FT process involves several key steps:

1. Syngas Production:
o Syngas is typically produced from natural gas, coal, biomass, or waste materials
through processes such as steam reforming, partial oxidation, or gasification.
o The syngas composition is adjusted to achieve the desired H₂/CO ratio, usually
around 2:1 for FT synthesis.
2. Syngas Conditioning:
o The syngas is purified to remove impurities like sulphur and nitrogen compounds
that can poison the FT catalyst.
o The water-gas shift reaction may be used to adjust the H₂/CO ratio:

CO + H2O → CO2 + H2
 3. Fischer-Tropsch Reaction:
o The purified syngas is fed into an FT reactor containing a catalyst, typically based
on iron or cobalt.
o The FT reaction converts syngas into a mixture of hydrocarbons, with the general
formula:

(2n+1)H2 + nCO → CnH2n+2 + nH2O Page | 26

4. Product Separation and Refining:

o The hydrocarbon products are separated into different fractions, such as gases,
naphtha, diesel, and waxes, using distillation and other separation techniques.
o Further refining and processing may be required to produce finished products
like fuels and lubricants.

Types of Fischer-Tropsch Reactors

1. Fixed Bed Reactors:

o Contains a catalyst packed in tubes or beds through which the syngas flow.
o Suitable for producing waxes and heavy hydrocarbons.
2. Fluidized Bed Reactors:
o Contain catalyst particles suspended by the upward flow of syngas.
o Offer good temperature control and are suitable for large-scale operations.
3. Slurry Bed Reactors:
o Contain catalyst suspended in a liquid hydrocarbon medium.
o Provide excellent heat management and are effective for producing a wide range
of hydrocarbons.

Fischer-Tropsch Catalysts

 Cobalt-Based Catalysts:
o Preferred for natural gas feedstocks due to higher activity and selectivity towards
long-chain hydrocarbons.
o More expensive but have a longer lifespan and higher resistance to poisoning.
 Iron-Based Catalysts:
o Preferred for coal or biomass feedstocks due to better tolerance to impurities and
ability to perform the water-gas shift reaction.
o Less expensive but may require more frequent regeneration.

Products of the Fischer-Tropsch Synthesis

1. FT Liquids:
o Diesel: High cetane number, low sulphur content, and good combustion
properties make FT diesel a premium fuel.
o Naphtha: Used as a feedstock for petrochemical production or blended into
gasoline.
o Jet Fuel: FT jet fuel meets stringent aviation standards and provides excellent
performance.
2. FT Waxes:
o Long-chain hydrocarbons can be used in various applications, including candles,
coatings, and lubricants.
3. Byproducts:
o Water: Produced as a byproduct and often requires treatment before disposal.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
o Light Hydrocarbons: Methane and other light gases can be used as fuel for power
generation or further processing.

Advantages of Fischer-Tropsch Synthesis

 Feedstock Flexibility: This can utilize a wide range of carbon-containing feedstocks,

enhancing energy security and flexibility.
 High-Quality Fuels: Produces fuels with superior properties, such as high-cetane
diesel and low-emission jet fuel.
 Environmental Benefits: When using biomass or waste feedstocks, FT synthesis can
contribute to reducing greenhouse gas emissions and managing waste.

Challenges and Considerations

 High Capital and Operating Costs: FT plants are capital-intensive and require
significant investment in purification and refining processes.
 Energy Intensity: The process is energy-intensive, particularly in the syngas
production and conditioning stages.
 Carbon Management: CO₂ emissions from syngas production need to be managed,
potentially through carbon capture and storage (CCS) technologies.

Industrial Applications

 Coal-to-Liquids (CTL): Converting coal into liquid fuels, often used in regions with
abundant coal reserves but limited oil resources.
 Gas-to-Liquids (GTL): Converting natural gas into liquid fuels, providing a way to
monetize stranded gas reserves and produce high-quality fuels.
 Biomass-to-Liquids (BTL): Converting biomass into liquid fuels, offering a
renewable and potentially carbon-neutral source of hydrocarbons.

HYDROFORMYLATION AND ITS UTILIZATION IN THE CHEMICAL INDUSTRY

Hydroformylation, also known as the oxo process, is a key industrial reaction in which an
alkene is converted into an aldehyde using synthesis gas (a mixture of carbon monoxide and
hydrogen). This reaction is catalyzed by metal complexes, typically involving transition metals
such as cobalt or rhodium. Hydroformylation is an important process in the chemical industry
due to its ability to produce aldehydes, which are versatile intermediates in the production of
alcohols, acids, and other valuable chemicals. Hydroformylation is a pivotal process in the
chemical industry, enabling the efficient conversion of alkenes to aldehydes and their
derivatives. The development of efficient catalysts, particularly rhodium-based systems, has
enhanced the selectivity and economic viability of this process. Hydroformylation plays a
critical role in producing a wide range of chemicals, from bulk industrial products like alcohols
and acids to fine chemicals for speciality applications.

Mechanism of Hydroformylation

The hydroformylation reaction can be summarized as follows:

R-CH=CH2 + CO + H2 → R-CH2CH2CHO

Here, an alkene (R-CH=CH₂) reacts with carbon monoxide (CO) and hydrogen (H₂) to form
an aldehyde (R-CH₂CH₂CHO).
The mechanism of hydroformylation involves several key steps:

1. Alkene Coordination:
o The alkene coordinates with the metal centre of the catalyst.
2. Insertion of CO:
o The coordinated alkene undergoes a migratory insertion with carbon monoxide
to form an acyl-metal complex. Page | 28
3. Hydrogenation:
o The acyl-metal complex is hydrogenated to form the aldehyde and regenerate the
catalyst.

Catalysts Used in Hydroformylation

1. Cobalt Catalysts:
o Historically, cobalt carbonyl complexes were the first catalysts used in
hydroformylation.
o They operate under higher temperatures (150-200 °C) and pressures (200-300
atm).
2. Rhodium Catalysts:
o Rhodium-based catalysts, such as HRh(CO)(PPh₃)₃, are more active and
selective than cobalt catalysts.
o They operate under milder conditions (80-120 °C and 1-10 atm).
o Rhodium catalysts offer higher selectivity towards linear aldehydes, which are
often more desirable.

Utilization in the Chemical Industry

Hydroformylation is widely used in the chemical industry for the production of various
aldehydes, which serve as intermediates for other valuable chemicals. Some of the key
applications include:

1. Production of Aldehydes:
o Butyraldehyde: Produced from propylene, used as an intermediate in the
production of butanol, 2-ethylhexanol, and plasticizers.
o Valeraldehyde: Produced from butenes, used in the synthesis of pentanol and
plasticizers.
o Hexanal: Produced from pentenes, used in the synthesis of hexanol and other
speciality chemicals.
2. Alcohol Production:
o Aldehydes produced via hydroformylation can be further hydrogenated to form
alcohols.
o For example, butyraldehyde can be hydrogenated to n-butanol, which is used as
a solvent and a feedstock for plasticizers.
3. Acid Production:
o Aldehydes can be oxidized to form carboxylic acids.
o For example, propionaldehyde can be oxidized to propionic acid, which is used
as a preservative and a feedstock for herbicides.
4. Plasticizers and Surfactants:
o Alcohols derived from hydroformylation products are key intermediates in the
production of plasticizers, which are used to enhance the flexibility of plastics.
o These alcohols are also used in the production of surfactants, which are used in
detergents and personal care products.
5. Fine Chemicals:
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
o Hydroformylation is used in the synthesis of various fine chemicals, including
flavours, fragrances, and pharmaceuticals.

Industrial Processes

Several industrial processes are based on hydroformylation, including:

1. OXO Process:
o The classic industrial process for hydroformylation primarily uses cobalt or
rhodium catalysts.
o Produces aldehydes from alkenes, which are then converted to alcohols or other
derivatives.
2. Shell Higher Olefin Process (SHOP):
o An integrated process that produces linear alpha olefins via ethylene
oligomerization and then converts them to aldehydes via hydroformylation.
3. Eastman Oxo Process:
o A variant of the hydroformylation process used by Eastman Chemical Company
focuses on the production of aldehydes and their subsequent conversion to
alcohols and other chemicals.

Advantages and Challenges

Advantages:

 Versatility: Can convert a wide range of alkenes to valuable aldehydes.

 High Selectivity: Rhodium catalysts offer high selectivity for linear aldehydes.
 Economic Efficiency: Produces key intermediates for various industrial chemicals
and materials.

Challenges:

 Catalyst Cost: Rhodium is expensive, making catalyst recovery and recycling

important.
 Process Conditions: Optimization of reaction conditions (temperature, pressure,
H₂/CO ratio) is crucial for maximizing yield and selectivity.
 Feedstock Purity: Impurities in the feedstock can poison the catalyst and reduce
efficiency.

CHEMISTRY AND APPLICATION OF WOOD PULPING

Wood pulping is the process of converting wood into pulp, which is the primary raw material
for papermaking. The pulp consists of cellulose fibres, which are separated from the lignin and
hemicellulose present in wood. There are several methods for producing wood pulp, each
involving different chemical processes and resulting in different types of pulp suited for various
applications. The main methods are mechanical pulping, chemical pulping, and semi-chemical
pulping. Wood pulping is a critical process in the production of paper and other cellulose-based
products. It involves various mechanical and chemical methods to separate cellulose fibres
from lignin and hemicellulose. Each method has its advantages and disadvantages, and the
choice of method depends on the desired properties of the final product. The pulp produced is
used in a wide range of applications, from everyday paper products to specialized industrial
materials. Sustainable practices and environmental considerations are increasingly important
in the industry to minimize the ecological footprint of pulping operations.
1. Mechanical Pulping

Mechanical pulping involves physically grinding wood to separate the fibres. There are two
primary methods: groundwood pulping and refiner mechanical pulping (RMP).

Groundwood Pulping
Page | 30
 Process: Wood logs are pressed against a rotating abrasive stone to grind the wood into
pulp.
 Advantages: High yield (about 90-95% of the original wood mass).
 Disadvantages: The pulp contains a high amount of lignin and other impurities,
resulting in lower strength and brightness. It is primarily used for newsprint and lower-
quality paper.

Refiner Mechanical Pulping (RMP)

 Process: Wood chips are fed between rotating discs (refiners) to mechanically separate
the fibres.
 Advantages: Higher quality than groundwood pulp, but still retains significant lignin
content.
 Disadvantages: Energy-intensive process.

2. Chemical Pulping

Chemical pulping involves using chemicals to dissolve lignin and hemicellulose, leaving behind
the cellulose fibres. The main chemical pulping processes are the Kraft process and the sulfite
process.

Kraft Pulping (Sulfate Process)

 Chemicals Used: Sodium hydroxide (NaOH) and sodium sulphide (Na₂S).

 Process: Wood chips are cooked in a "white liquor" (a mixture of NaOH and Na₂S) in
a digester under high temperature and pressure. The chemicals break down lignin and
hemicellulose, freeing the cellulose fibres.
 Advantages: Produces strong and high-quality pulp. It is the most widely used pulping
method. The process allows for chemical recovery and reuse.
 Disadvantages: Produces a dark-coloured pulp that requires bleaching for white
paper products. The process releases odorous sulfur compounds.

Sulphite Pulping

 Chemicals Used: Sulphurous acid (H₂SO₃) and bisulphite ions (HSO₃⁻).

 Process: Wood chips are cooked in a solution of sulfurous acid and bisulfite ions. The
chemicals break down lignin and hemicellulose.
 Advantages: Produces a lighter-coloured pulp than the Kraft process. Can be used to
produce specialty papers.
 Disadvantages: Less strength in the final pulp compared to Kraft pulp. More difficult
to recover chemicals for reuse.

3. Semi-Chemical Pulping

Semi-chemical pulping combines mechanical and chemical processes. The wood chips are
partially treated with chemicals to soften the lignin before mechanical refining.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 Process: Wood chips are partially cooked with chemicals (similar to Kraft or sulfite
processes) and then mechanically refined.
 Advantages: Higher yield than purely chemical pulping and produces stronger pulp
than purely mechanical methods.
 Disadvantages: Energy-intensive and requires handling of chemicals.

Applications of Wood Pulping

1. Paper and Paperboard Production

 Newsprint: Typically produced using mechanical pulps.

 Writing and Printing Paper: Made from chemical pulps, especially bleached Kraft
pulp.
 Packaging Materials: Kraft pulp is commonly used due to its strength.
 Tissue and Towel Products: Produced from both chemical and mechanical pulps,
often with additional treatments for softness and absorbency.

2. Specialty Papers

 Filter Papers: High-purity pulps are used for laboratory and industrial filters.
 Cigarette Paper: Requires specific properties achieved through tailored pulping
processes.
 Currency Paper: Strong and durable paper produced from high-quality pulps.

3. Dissolving Pulp

 Production of Rayon and Cellophane: Dissolving pulp is a highly purified form of

cellulose used as a raw material for cellulose derivatives.
 Cellulose Acetate: Used in producing photographic films, textiles, and plastics.

Environmental Considerations

 Chemical Recovery: The Kraft process has an efficient chemical recovery system that
reduces waste and environmental impact.
 Effluent Treatment: Both chemical and mechanical pulping processes produce
wastewater that requires treatment to remove organic and inorganic contaminants.
 Sustainable Forestry: Responsible sourcing of wood from sustainably managed
forests helps reduce the environmental impact of pulping.

Question: Describe the processes involved during Kraft pulping, giving chemical
equations where applicable.

The Kraft pulping process, also known as the sulfate process, is the most common method for
producing wood pulp. It involves the use of a highly alkaline solution (white liquor) to break
down lignin and hemicellulose, freeing the cellulose fibres. The main stages of the Kraft pulping
process include wood preparation, cooking, washing, and chemical recovery.

1. Wood Preparation

 Debarking: Logs are debarked to remove bark, which can contain impurities and
lower the quality of the pulp.
  Chipping: The debarked logs are cut into small, uniform wood chips to ensure even
cooking.

2. Cooking (Digestion)

The wood chips are cooked in a digester with white liquor, which is a mixture of sodium
hydroxide (NaOH) and sodium sulfide (Na₂S). This process, known as cooking or digestion, Page | 32
occurs under high temperatures (150-170 °C) and pressure (6-10 atm).

Chemical Reactions

 Degradation of Lignin: The alkaline conditions break down lignin, the complex
polymer that binds cellulose fibres together. The key reactions involve the cleavage of
ether bonds and the sulfonation of lignin fragments:

Lignin-O-R + NaOH → Lignin-O-Na + ROH

Lignin + Na2S → Lignin-S-Na + Other Fragments

 Degradation of Hemicellulose: Hemicelluloses are also partially degraded and

dissolved during the cooking process:

Hemicellulose + NaOH → Soluble Sugars + Other Compounds

3. Washing

After cooking, the pulp mixture (called brown stock) contains cellulose fibres, dissolved lignin,
hemicellulose, and spent cooking chemicals (black liquor). The pulp is washed to remove the
black liquor, which contains dissolved organic materials and spent chemicals.

4. Screening and Cleaning

The washed pulp is screened and cleaned to remove any remaining wood chips, knots, and
other impurities. This ensures that the pulp is uniform and of high quality.

5. Bleaching (Optional)

For producing white paper products, the pulp is bleached to remove the residual lignin and
achieve the desired brightness. Bleaching can involve several stages using chemicals such as
chlorine dioxide (ClO₂), oxygen (O₂), hydrogen peroxide (H₂O₂), and ozone (O₃).

6. Chemical Recovery

The Kraft process includes an efficient chemical recovery system to minimize waste and
recycle the cooking chemicals.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Recovery of Chemicals

 Concentration of Black Liquor: The black liquor is concentrated in evaporators to

increase its solids content.
 Combustion in Recovery Boiler: The concentrated black liquor is burned in a
recovery boiler to generate energy and produce smelt containing sodium carbonate
(Na₂CO₃) and sodium sulphide (Na₂S):

CnHmOpSq + O2 → Na2CO3 + Na2S + CO2 + H2O + Heat

 Causticizing: The smelt is dissolved in water to form green liquor, which is then
reacted with lime (CaO) in a causticizer to regenerate white liquor:

Na2CO3 + CaO + H2O → 2NaOH + CaCO3

Na2S + H2O → 2NaOH + H2S

 Lime Kiln: The calcium carbonate (CaCO₃) formed in the causticizing step is calcined
in a lime kiln to regenerate lime:

CaCO3 → CaO + CO2

Summary of the Kraft Pulping Process

1. Wood Preparation: Logs are debarked and chipped.

2. Cooking: Wood chips are cooked with white liquor (NaOH and Na₂S) to break down
lignin and hemicellulose, freeing cellulose fibres.
3. Washing: The pulp is washed to remove black liquor.
4. Screening and Cleaning: The pulp is screened and cleaned to remove impurities.
5. Bleaching (Optional): The pulp is bleached to achieve the desired brightness.
6. Chemical Recovery: Spent cooking chemicals are recovered and regenerated for
reuse.

The Kraft pulping process is highly efficient and produces strong, high-quality pulp suitable
for a wide range of paper and paperboard products. Its ability to recover and reuse chemicals
makes it economically viable and environmentally friendly.

Question: Describe the processes involved during sulphite pulping, giving

chemical equations where applicable.

Papermaking uses sulphite pulping, a chemical process that creates wood pulp. In order to
break down the lignin and hemicellulose and leave behind cellulose fibres, it entails boiling
wood chips in an acidic solution of sulphur dioxide (SO₂) and water, frequently with the aid of
other chemicals. Sulphite pulping involves the following steps: pretreatment of the wood,
cooking, washing, bleaching, and chemical recovery.

1. Wood Preparation

Debarking

 Process: Logs are debarked to remove bark, which can contain impurities and lower
the quality of the pulp.
Chipping

 Process: The debarked logs are cut into small, uniform wood chips to ensure even
cooking.

2. Cooking (Digestion)
Page | 34
The wood chips are cooked in a digester with a solution of sulfurous acid (H₂SO₃) and bisulfite
ions (HSO₃⁻). This solution is known as the cooking liquor. The cooking process occurs under
high temperature (130-160°C) and pressure (6-8 atm).

Chemical Reactions

 Formation of Sulfurous Acid:

SO2 + H2O → H2SO3

 Formation of Bisulfite Ions:

H2SO3 → H+ + HSO3−

 Degradation of Lignin: The acidic conditions break down lignin through sulfonation,
making it soluble in water:

Lignin + HSO3− → Lignin-SO3− + Other Fragments

3. Washing

After cooking, the pulp mixture (called brown stock) contains cellulose fibers, dissolved lignin,
hemicellulose, and spent cooking chemicals. The pulp is washed to remove the spent cooking
liquor, which contains dissolved organic materials and spent chemicals.

4. Screening and Cleaning

The washed pulp is screened and cleaned to remove any remaining wood chips, knots, and
other impurities. This ensures that the pulp is uniform and of high quality.

5. Bleaching

To produce white paper products, the pulp is bleached to remove the residual lignin and
achieve the desired brightness. Bleaching in sulphite pulping can involve several stages using
chemicals such as chlorine dioxide (ClO₂), oxygen (O₂), hydrogen peroxide (H₂O₂), and ozone
(O₃).

6. Chemical Recovery

The sulphite process includes a chemical recovery system to minimize waste and recycle the
cooking chemicals. However, the recovery process is less efficient than in the Kraft process.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Recovery of Chemicals

Recovery Boiler

 Combustion: The concentrated black liquor is burned in a recovery boiler to generate

energy and produce a smelt containing sodium carbonate (Na₂CO₃) and sodium
sulfide (Na₂S):

CnHmOpSq + O2 → Na2CO3 + Na2S + CO2 + H2O + Heat

Chemical Recovery and Reuse

 Lime Kiln: The sodium carbonate (Na₂CO₃) formed in the recovery boiler is converted
back into sodium hydroxide (NaOH) in a lime kiln:

Na2CO3 + CaO → 2NaOH + CaCO3

Summary of Sulphite Pulping Process

1. Wood Preparation: Logs are debarked and chipped.

2. Cooking: Wood chips are cooked with a bisulfite solution (H₂SO₃ and HSO₃⁻) under
high temperature and pressure to break down lignin and hemicellulose, freeing the
cellulose fibers.
3. Pulp Washing: The pulp is washed to remove the black liquor.
4. Screening and Cleaning: The pulp is screened and cleaned to remove impurities.
5. Bleaching (Optional): The pulp is bleached to achieve the desired brightness.
6. Chemical Recovery: Spent cooking chemicals are recovered and reused.

The sulphite pulping process produces pulp that is generally lighter in color and more easily
bleached than Kraft pulp, making it suitable for high-quality paper products. However, it is less
common than the Kraft process due to higher chemical costs and more challenging recovery
processes.

Question: What are the three primary components of wood pulp?

Wood composition
 Cellulose: Cellulose is a polymer (C6H10O5) that can crystallise to form very strong fibres.
 Lignin: Lignin is also a polymer but is typically in an amorphous form.
 Hemicellulose: Hemicellulose is a partly crystalline polymer that also acts as a matrix or binder.

PAPER MAKING PROCESS

(Inherent question: Name and explain the five stages of paper making process.)

The paper-making process consists of five main stages: pulping, refining, sheet formation,
pressing, and drying. Each stage plays a crucial role in transforming raw materials into finished
paper. Here is a detailed description of each stage:
1. Pulping

Objective: To convert raw materials (wood, recycled paper, etc.) into pulp, which consists of
cellulose fibers.

Processes:
Page | 36
 Mechanical Pulping: Wood chips are mechanically ground to separate the fibers. This
method yields high fiber recovery but can damage the fibers and retain lignin, making
the paper less durable and prone to yellowing.
 Chemical Pulping: Uses chemicals to dissolve lignin and separate the fibers. The most
common methods are Kraft and sulphite pulping. Chemical pulping produces stronger
and more durable paper.
 Recycled Pulping: Recycled paper is mixed with water and mechanical action to
separate the fibers. Ink and contaminants are removed through deinking and cleaning
processes.

2. Refining

Objective: To improve the fiber quality and prepare the pulp for sheet formation.

Processes:

 Beating and Refining: Pulp is passed through refiners where the fibers are
mechanically treated. This process fibrillates (creates tiny fibrils on the surface of) the
fibers, improving their bonding ability and enhancing paper strength, flexibility, and
smoothness.
 Additives: Chemicals such as fillers, sizing agents, and colorants may be added to the
pulp to impart desired properties to the final paper product.

3. Sheet Formation

Objective: To form a continuous web of paper from the prepared pulp.

Processes:

 Fourdrinier Machine: The most common machine for sheet formation. The diluted
pulp (about 99% water and 1% fiber) is fed onto a moving mesh wire screen. Water
drains through the screen, leaving a mat of fibers.
 Cylinder Machine: Uses rotating cylinders partially submerged in pulp vats. As the
cylinders rotate, they pick up a layer of fibers, which is transferred to a moving felt belt
to form the sheet.
 Twin-Wire Forming: Pulp is injected between two moving wire screens, enhancing
water removal and improving sheet formation.

4. Pressing

Objective: To remove water from the paper web and consolidate the fibers.

Processes:

 Press Section: The wet paper web passes through a series of press rolls that squeeze
out water and increase fiber bonding. This reduces the water content to about 50-60%.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 Felt Belts: The web is carried by felt belts, which also help absorb water and smooth
the paper surface.

5. Drying

Objective: To remove the remaining water from the paper web and achieve the desired
moisture content.

Processes:

 Dryer Section: The paper web passes over a series of heated cylinders or drums that
evaporate the water. The temperature and drying speed are carefully controlled to
prevent paper defects like curling or shrinking.
 Final Moisture Adjustment: After the main drying process, the paper may pass
through additional equipment like steam showers or air dryers to fine-tune the moisture
content.

Finishing (Optional)

Objective: To provide the final properties and appearance to the paper.

Processes:

 Calendaring: The paper passes through a series of rollers (calenders) to smooth and
gloss the surface, improve thickness uniformity, and enhance printability.
 Coating: A coating mixture (containing pigments, binders, and additives) is applied to
one or both sides of the paper to improve surface properties like brightness, smoothness,
and ink receptivity.
 Cutting and Reeling: The finished paper is cut into sheets or wound into large rolls,
depending on the end-use requirements.

In summary, the five main stages of the paper-making process are:

1. Pulping: Converting raw materials into pulp through mechanical, chemical, or

recycled methods.
2. Refining: Improving fiber quality and adding chemicals to prepare the pulp for sheet
formation.
3. Sheet Formation: Forming a continuous paper web from the prepared pulp using
machines like the Fourdrinier or cylinder machine.
4. Pressing: Removing water and consolidating fibers by passing the web through press
rolls.
5. Drying: Evaporating the remaining water and achieving the desired moisture content
using heated cylinders or drums.

Optional finishing processes like calendaring and coating may be used to enhance the paper's
final properties and appearance.

INDUSTRIAL PROCESSES INVOLVING OILS AND FATS

Food, medicine, cosmetics, and biofuels are just a few of the businesses that depend on the vast
range of industrial operations utilising oils and fats. These procedures seek to extract, purify,
alter, and employ fats and oils for particular uses. Oil and fat-related industrial operations are
essential to numerous industries, producing everything from food to biofuels and industrial
lubricants. The raw ingredients are obtained by extraction techniques such as solvent and
mechanical extraction, after which they are processed to eliminate impurities. Hydrogenation
and interesterification are two examples of modifications that modify fats' chemical and
physical characteristics to suit particular uses. Oils and fats are essential in both the culinary
and non-food industries because of their versatility. The following is a summary of important
industrial procedures involving fats and oils: Page | 38

1. Extraction of Oils and Fats

Mechanical Extraction

 Cold Pressing: Seeds or nuts are mechanically pressed to extract oil without heating.
This method preserves natural flavours and nutrients, producing high-quality oils like
extra virgin olive oil.
 Expeller Pressing: Uses mechanical pressure and heat to extract oil from seeds or
nuts. It is more efficient than cold pressing but may degrade some nutrients.

Solvent Extraction

 Process: Seeds or nuts are ground and treated with a solvent (usually hexane) to
dissolve the oil. The oil-solvent mixture is then separated, and the solvent is evaporated
and recovered.
 Advantages: Higher oil yield compared to mechanical extraction.
 Disadvantages: Requires solvent recovery and poses potential environmental and
health risks.

Question: Discuss solvents that extract both polar and non-polar lipids from
seeds, nuts and other materials stating the reason for their effectiveness.

Response: It is necessary for solvents to be able to dissolve a broad variety of lipid types
in order to extract both polar and non-polar lipids from oilseeds. The following typical
solvents are useful for removing both polar and non-polar lipids:

1. Chloroform-Methanol Mixture

 Ratio: Typically used in a 2:1 (chloroform) ratio.

 Why is it effective? Chloroform is non-polar and dissolves non-polar lipids (like
triglycerides and sterols), while methanol is polar and helps dissolve polar lipids (like
phospholipids). Together, they provide a broad-spectrum extraction.

2. Ethanol

 Why is it effective? Ethanol has both polar and non-polar characteristics, making it
effective for extracting a wide range of lipid classes, including both polar and non-polar
lipids.

3. Hexane-Isopropanol Mixture

 Ratio: Often used in a 3:2 (hexane) ratio.

 Why is it effective? Hexane is non-polar, which is excellent for extracting non-polar
lipids, while isopropanol has polar characteristics, allowing for the extraction of polar
lipids.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
4. Diethyl Ether

 Why is it effective? Diethyl ether is slightly polar but still non-polar enough to
dissolve a wide range of lipids, making it suitable for extracting both polar and non-
polar lipids.

5. Acetone

 Why is it effective? Acetone is moderately polar and can dissolve a range of polar and
non-polar lipids, making it useful for comprehensive lipid extraction.

6. Butanol-Hexane Mixture

 Ratio: Commonly used in a 1:1 (butanol) ratio.

 Why is it effective? Butanol is polar, while hexane is non-polar, providing a balance
that can extract both types of lipids effectively.

In summary, For thorough lipid extraction from oilseeds, the chloroform-methanol

mixture is one of the most used solvent systems, but butanol-hexane and hexane-
isopropanol combinations are also useful. The particular lipid profile, as well as the
planned analysis or application, determine which solvent system is best.

Question: Discuss solvents used to extract oils in the industry stating their
advantages and applications.

Response: In the sector, oils from seeds, nuts, and other raw materials are extracted
using a variety of solvents. Various criteria, such as the kind of oil, the raw material, and
the desired level of purity in the finished product, influence the choice of solvent. The
following list includes some typical industrial solvents used in oil extraction:

1. Hexane (C6H14):
o Most Common: Hexane is the most widely used solvent in the oil extraction
industry due to its efficiency and low cost.
o Advantages: It has a high selectivity for non-polar compounds like oils, making
it very effective at extracting oils from seeds and other raw materials.
o Applications: Commonly used for extracting soybean oil, canola oil, corn oil,
and other vegetable oils.
2. Ethanol (CH3CH2OH):
o Advantages: Ethanol is considered safer and more environmentally friendly
compared to hexane. It is also suitable for extracting oils that are intended for
food or cosmetic use.
o Applications: Often used for extracting essential oils, herbal oils, and in
processes where the purity of the oil is critical.
3. Petroleum Ether:
o Advantages: Similar to hexane in terms of its ability to dissolve oils, petroleum
ether is used in some cases as a substitute for hexane.
o Applications: Used in laboratory settings and some industrial processes for
extracting oils from seeds and plant materials.

Question: What do you understand by the term 'petroleum ether'?

Response: Petroleum ether is a term used to describe a group of volatile, highly

flammable hydrocarbons derived from petroleum. Despite the name, it is not an
 "ether" in the chemical sense but rather a mixture of aliphatic hydrocarbons,
primarily alkanes (such as pentane, hexane, and heptane). It is commonly used as a
non-polar solvent in laboratories and various industrial processes.

Or

One word used to characterise a class of very flammable, volatile hydrocarbons Page | 40
generated from petroleum is petroleum ether. In spite of its name, it is a combination
of aliphatic hydrocarbons, mostly alkanes (such pentane, hexane, and heptane),
rather than a "ether" in the chemical sense. Often employed in labs and other
industrial processes, it is a non-polar solvent.

Key Characteristics of Petroleum Ether:

1. Composition:
o Petroleum ether is a complex mixture of hydrocarbons with boiling ranges
typically between 30°C to 60°C or 60°C to 80°C, depending on the grade.
o The exact composition can vary, but it generally includes lower alkanes such as
pentane (C₅H₁₂), hexane (C₆H₁₄), and heptane (C₇H₁₆).
2. Properties:
o Low Boiling Point: Petroleum ether is characterized by its low boiling point,
making it highly volatile.
o Non-Polar Solvent: It is a non-polar solvent, which means it is particularly
effective at dissolving non-polar compounds like fats, oils, and waxes.
o Flammability: Highly flammable due to its low flash point and high volatility,
requiring careful handling and storage.
o Odour: It has a characteristic, strong odor associated with many hydrocarbon
solvents.
3. Uses:
o Solvent Extraction: Used in the extraction of oils, fats, and other non-polar
compounds from plant materials or other sources.
o Laboratory Solvent: Commonly used in laboratories for recrystallization,
chromatography, and as a solvent in chemical reactions where a non-polar
environment is needed.
o Cleaning and Degreasing: Sometimes used as a degreasing agent or in
cleaning applications where its non-polar nature is advantageous.
4. Health and Safety:
o Toxicity: Petroleum ether can be toxic if inhaled, ingested, or absorbed
through the skin. Prolonged exposure can lead to respiratory, neurological, and
other health issues.
o Handling: It should be handled with care, using appropriate personal
protective equipment (PPE) and in well-ventilated areas to minimize inhalation
risks.
5. Environmental Impact:
o Volatile Organic Compounds (VOCs): As a volatile organic compound,
petroleum ether contributes to air pollution and can have environmental
impacts if not managed properly.

Petroleum ether is a volatile, non-polar solvent derived from petroleum, primarily

used in laboratory and industrial applications. Its properties make it particularly
suitable for dissolving non-polar substances like oils and fats. Despite its name, it is
not an ether but a mixture of low-boiling aliphatic hydrocarbons. Due to its
flammability and potential health risks, it must be handled with caution.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES

4. Supercritical CO₂ (Carbon Dioxide): (Supercritical CO₂ is a state of carbon dioxide

that occurs when it is subjected to a temperature and pressure above its critical point.
In this supercritical state, CO₂ exhibits unique properties that are intermediate between
those of a liquid and a gas. This makes it an extremely versatile and useful solvent in
various industrial applications, including extraction processes.

Key Properties of Supercritical CO₂: Density: Supercritical CO₂ has a density

similar to that of a liquid, which allows it to dissolve substances effectively, including
oils, fats, and other compounds. Viscosity: Its viscosity is closer to that of a gas, which
means it can penetrate materials more easily than a liquid could. This allows it to extract
compounds from solid matrices efficiently. Diffusivity: The diffusivity of supercritical
CO₂ is higher than that of a liquid, meaning it can transport molecules more rapidly.
Adjustable Solvent Power: The solvent power of supercritical CO₂ can be finely
tuned by adjusting the temperature and pressure. This allows for selective extraction of
specific compounds by changing these parameters.

Critical Point of CO₂:

 Critical Temperature: 31.1°C (88°F)

 Critical Pressure: 7.38 MPa (about 1,071 psi)

Above these conditions, CO₂ becomes supercritical, and its unique properties come
into play.

Applications of Supercritical CO₂:

1. Extraction of Essential Oils: Supercritical CO₂ is used to extract essential oils from
plants. This method is preferred in the food, pharmaceutical, and cosmetic industries
because it leaves no solvent residues and preserves the quality and aroma of the oils. It's
also used in the extraction of certain food-grade oils.
2. Decaffeination of Coffee and Tea: Supercritical CO₂ is used to remove caffeine
from coffee beans and tea leaves. The process is highly selective, leaving the flavor
compounds largely intact.
3. Extraction of Natural Products: It's used to extract natural compounds such as
flavors, fragrances, and nutraceuticals from various plant materials.
4. Polymer Processing: Supercritical CO₂ is used in processes like polymer
impregnation, foaming, and particle formation due to its ability to act as a plasticizer
and its tunable solvent properties.
5. Environmental Applications: Supercritical CO₂ is also employed in environmental
applications like soil remediation and waste treatment, where it can be used to extract
contaminants from soils and sediments.
6. Pharmaceuticals: In the pharmaceutical industry, supercritical CO₂ is used for the
purification of compounds, micronization of drugs, and creation of nanoparticles.

Advantages of Supercritical CO₂:

 Non-toxic and Non-flammable: It is a safer alternative to traditional organic

solvents. Supercritical CO₂ is a clean, non-toxic, and non-flammable solvent that is
considered environmentally friendly. It is highly efficient and can extract oils
without leaving any solvent residues
  Environmentally Friendly: CO₂ is readily available and can be recycled within
the process, minimizing waste.
 No Residues: Unlike organic solvents, supercritical CO₂ leaves no residue, which
is particularly important in food and pharmaceutical applications.

Disadvantages of Supercritical CO₂:

Page | 42
 High Equipment Costs: The equipment required to maintain CO₂ in a
supercritical state is expensive and requires precise control of temperature and
pressure.
 Energy Intensive: Achieving and maintaining the supercritical state requires
significant energy input, particularly for the compression of CO₂.

Supercritical CO₂ extraction is valued for its ability to produce high-purity extracts
without the use of harmful solvents, making it a preferred method in industries
where product quality and safety are paramount.

Question: Explain the term 'Supercritical CO2'.

Response: Supercritical CO₂ (Carbon Dioxide) refers to a state of carbon dioxide that
occurs when it is subjected to conditions above its critical temperature and pressure. In this
state, CO₂ exhibits properties that are intermediate between those of a liquid and a gas, which
makes it an exceptional solvent for various industrial applications.

Critical Point of CO₂:

 Critical Temperature: 31.1°C (88°F)

 Critical Pressure: 7.38 MPa (approximately 1,071 psi)

At temperatures and pressures above these critical values, CO₂ enters the supercritical state,
where it behaves differently from both gases and liquids.

Properties of Supercritical CO₂:

1. Density: Supercritical CO₂ has a density similar to that of a liquid, allowing it to

dissolve substances effectively. Its density can be adjusted by changing the pressure,
which influences its solvating power.
2. Viscosity: Its viscosity is closer to that of a gas, which enables it to diffuse through
materials easily, similar to how gases spread through spaces.
3. Diffusivity: Supercritical CO₂ has high diffusivity, meaning it can penetrate and
interact with materials more effectively than a liquid solvent.
4. Solvent Power: The solvating ability of supercritical CO₂ can be finely tuned by
adjusting temperature and pressure. This allows for selective extraction of specific
compounds.
5. Non-Toxic and Non-Flammable: It is relatively safe compared to many organic
solvents, as it is non-toxic and non-flammable under standard handling conditions.
6. Low Surface Tension: The low surface tension of supercritical CO₂ allows it to
interact with materials at the molecular level, making it useful for processes that
require fine control over solubility and extraction.

Applications of Supercritical CO₂:

1. Extraction:
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
o Essential Oils: Used to extract essential oils from plants, preserving the
delicate compounds and aromas without leaving solvent residues.
o Caffeine Removal: Employed in the decaffeination of coffee and tea. The
process selectively removes caffeine while retaining flavor compounds.
2. Pharmaceuticals:
o Purification: Used to purify pharmaceutical compounds and to create fine
powders of drugs.
o Nanoparticle Formation: Employed in creating nanoparticles for drug
delivery systems.
3. Food Industry:
o Flavor Extraction: Extracts flavors and fragrances from food products
without altering their taste profiles.
o Preservation: Used in processes to preserve food products and ingredients.
4. Environmental:
o Soil Remediation: Helps in cleaning contaminated soils by extracting
pollutants.
o Waste Treatment: Utilized in various waste treatment processes to extract
and purify substances.
5. Polymer Processing:
o Polymer Impregnation: Used to impregnate polymers with other
substances.
o Foaming: Used in producing polymer foams and creating porous materials.

Advantages of Supercritical CO₂:

 Environmentally Friendly: It is a greener alternative to many organic solvents,

with minimal environmental impact and the ability to be recycled within the process.
 No Residue: Leaves no solvent residue, which is especially important in food and
pharmaceutical applications.
 Efficient: Provides effective and selective extraction, often with lower energy
requirements compared to other methods.

Disadvantages:

 High Equipment Costs: Requires specialized, high-pressure equipment, which can

be expensive.
 Energy Intensive: The process requires significant energy to maintain the CO₂ in its
supercritical state, particularly for compression and heating.

Summary:

Supercritical CO₂ is a state of carbon dioxide achieved at high temperatures and pressures
where it possesses unique solvent properties. It is widely used in various industries for its
effectiveness in extracting, purifying, and processing substances, while being safer and more
environmentally friendly than many traditional organic solvents.

5. Isopropanol (Isopropyl Alcohol):

o Advantages: Another alcohol-based solvent that is occasionally used for oil
extraction is isopropanol, especially in situations where methanol or ethanol may
not be appropriate.
 oApplications: Used for extracting oils in laboratory and industrial settings,
particularly where a lower polarity solvent is needed.
6. Acetone:
o Advantages: Acetone is a powerful solvent that can be used for oil extraction,
especially when dealing with certain plant materials.
o Applications: Less commonly used than hexane or ethanol, but still relevant in
some specialized oil extraction processes. Page | 44
7. Methanol:
o Advantages: Methanol is highly effective at dissolving oils and is sometimes
used in combination with other solvents.
o Applications: Used in specific industrial processes where its properties are
required, but less common for food-grade oil extraction due to its toxicity.
8. Butane:
o Advantages: Butane is a hydrocarbon solvent that is frequently used to extract
some plant oils, especially when making concentrates like cannabis oils.
o Applications: Used in the extraction of essential oils and other high-value plant
extracts.

These solvents are selected according to a number of criteria, including the kind of oil
being extracted, the solvent's effectiveness, cost, safety, and environmental effects.
Because of worries about the effects traditional solvents like hexane have on the
environment and human health, several companies are shifting more and more towards
greener solvents like ethanol and supercritical CO2.

2. Refining of Oils and Fats

Refining improves the quality of crude oils by removing impurities, free fatty acids, and other
undesirable components.

Degumming

 Process: Removes phospholipids and other hydratable impurities using water or acid
treatment.
 Equation:

Phospholipids + H2O → Hydrated Phospholipids (Gums)

Neutralization

 Process: Free fatty acids (FFA) are neutralized using an alkali (usually sodium
hydroxide, NaOH) to form soaps, which are then removed.
 Equation:

RCOOH (Fatty Acid) + NaOH → RCOONa (Soap) +H2O

Bleaching

 Process: Removes pigments, trace metals, and oxidation products using adsorbents
like activated clay or carbon.
 Advantages: Improves oil colour and stability.

Deodorization
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 Process: Steam distillation at high temperatures under vacuum to remove volatile
compounds that cause odours and flavours.
 Advantages: Produces neutral-tasting and smelling oil.

3. Modification of Oils and Fats

Hydrogenation

 Process: Unsaturated fats are hydrogenated to make them more saturated, increasing
stability and altering melting points.
 Catalyst: Typically nickel.
 Equation:

RCH = CHR + H2 → RCH2CH2R

 Application: Used to produce margarine and shortening.

Interesterification

 Process: Rearranges fatty acids on the glycerol backbone to alter melting properties
and functionality.
 Catalysts: Chemical (sodium methoxide) or enzymatic (lipase).
 Application: Produces fats with specific melting characteristics for use in
confectionery and baking.

Fractionation

 Process: Separates oil into solid (stearin) and liquid (olein) fractions by controlled
cooling and filtration.
 Application: Used to produce speciality fats like cocoa butter substitutes.

4. Utilization of Oils and Fats

Food Industry
 Cooking Oils: Vegetable oils like canola, soybean, and sunflower oil.
 Margarine and Shortening: Produced by hydrogenation and interesterification.
 Confectionery Fats: Specialty fats with specific melting points for chocolate and other
confections.

Non-Food Applications
 Cosmetics and Personal Care: Oils and fats are used in creams, lotions, and soaps
for their moisturizing properties.
 Pharmaceuticals: Used as carriers for active ingredients in drug formulations.
 Biofuels: Biodiesel is produced from vegetable oils and animal fats through
transesterification.

Transesterification for Biodiesel Production

 Process: Oils or fats react with methanol or ethanol in the presence of a catalyst
(usually sodium or potassium hydroxide) to produce methyl or ethyl esters (biodiesel)
and glycerol.
 Equation:

Triglyceride + 3ROH → 3RCOOR (Biodiesel) + Glycerol

  Advantages: Provides a renewable alternative to fossil fuels.

FATTY ACID COMPOSITION OF SOME VEGETABLE OILS

The fatty acid composition of vegetable oils varies widely depending on the source of the oil.
The fatty acid profiles provided here give an idea of the predominant fatty acids in each type of
oil, influencing their uses in cooking, food processing, and industrial applications. Here is a Page | 46
summary of the fatty acid composition of some common vegetable oils:

1. Palm Kernel Oil

 Lauric Acid (C12:0): 45-55%

 Myristic Acid (C14:0): 15-20%
 Palmitic Acid (C16:0): 7-10%
 Oleic Acid (C18:1): 12-20%
 Linoleic Acid (C18:2): 1-3%

2. Coconut Oil

 Lauric Acid (C12:0): 45-52%

 Myristic Acid (C14:0): 16-21%
 Palmitic Acid (C16:0): 7-10%
 Oleic Acid (C18:1): 5-8%
 Linoleic Acid (C18:2): 1-2%

3. Olive Oil

 Oleic Acid (C18:1): 55-83%

 Linoleic Acid (C18:2): 3.5-21%
 Palmitic Acid (C16:0): 7.5-20%
 Stearic Acid (C18:0): 0.5-5%
 Linolenic Acid (C18:3): 0-1.5%

4. Soybean Oil

 Linoleic Acid (C18:2): 51%

 Oleic Acid (C18:1): 23%
 Palmitic Acid (C16:0): 10%
 Stearic Acid (C18:0): 4%
 Linolenic Acid (C18:3): 7-10%

5. Sunflower Oil

 Linoleic Acid (C18:2): 48-74%

 Oleic Acid (C18:1): 14-40%
 Palmitic Acid (C16:0): 4-9%
 Stearic Acid (C18:0): 1-7%
 Linolenic Acid (C18:3): 0-1%

6. Canola (Rapeseed) Oil

 Oleic Acid (C18:1): 53-63%

 Linoleic Acid (C18:2): 19-21%
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
 Linolenic Acid (C18:3): 7-11%
 Palmitic Acid (C16:0): 2.5-6%
 Stearic Acid (C18:0): 1-2.5%
 Eicosenoic Acid (C20:1): 1%

7. Corn Oil

 Linoleic Acid (C18:2): 34-65%

 Oleic Acid (C18:1): 20-42%
 Palmitic Acid (C16:0): 8-12%
 Stearic Acid (C18:0): 1-4%
 Linolenic Acid (C18:3): 0-1%

8. Peanut Oil

 Oleic Acid (C18:1): 37-72%

 Linoleic Acid (C18:2): 13-43%
 Palmitic Acid (C16:0): 6-12%
 Stearic Acid (C18:0): 1-6%
 Arachidic Acid (C20:0): 1-2%
 Behenic Acid (C22:0): 1-3%

9. Palm Oil

 Palmitic Acid (C16:0): 32-45%

 Oleic Acid (C18:1): 38-50%
 Linoleic Acid (C18:2): 5-11%
 Stearic Acid (C18:0): 4-5%
 Myristic Acid (C14:0): 1%

10. Cottonseed Oil

 Linoleic Acid (C18:2): 50-55%

 Oleic Acid (C18:1): 15-20%
 Palmitic Acid (C16:0): 22-26%
 Stearic Acid (C18:0): 2-4%
 Linolenic Acid (C18:3): 0-1%

In summary, vegetable oils contain varying compositions of saturated and unsaturated fatty
acids, which affect their physical and nutritional properties. Saturated fatty acids such as lauric,
myristic, palmitic, and stearic acids contribute to the solidity and shelf stability of the oils, while
unsaturated fatty acids such as oleic, linoleic, and linolenic acids contribute to fluidity and
health benefits.

THE PRODUCTION OF SOAP FROM PALM KERNEL OIL

The production of soap from palm kernel oil involves several key steps, including
saponification, mixing, molding, curing, and packaging. Palm kernel oil is rich in lauric acid,
which makes it a valuable raw material for producing hard soaps with good lathering
properties. Here is a detailed description of each step in the process:

1. Saponification
Objective: To convert palm kernel oil into soap through a chemical reaction with an alkali.

Processes:

 Preparation of Raw Materials:

o Palm Kernel Oil: The primary fat/oil used in the process.
o Alkali: Typically sodium hydroxide (NaOH) for bar soap or potassium hydroxide Page | 48
(KOH) for liquid soap.
o Water: Used to dissolve the alkali and facilitate the saponification reaction.
 Saponification Reaction: The triglycerides in palm kernel oil react with the alkali to
form soap and glycerol.

Triglyceride + 3NaOH → Glycerol + 3Soap

The general equation can be represented as:

C3H5(COOR)3 + 3NaOH → C3H5(OH)3 + 3RCOONa

Where:

o C₃H₅(COOR)₃ represents the triglyceride.

o RCOONa represents the soap (sodium salt of fatty acid).
o C₃H₅(OH)₃ represents the glycerol.
 Process:
o Heating: The palm kernel oil is heated in a large kettle or saponification vessel.
o Alkali Solution: A solution of NaOH (for solid soap) or KOH (for liquid soap)
is prepared by dissolving the alkali in water.
o Mixing: The alkali solution is slowly added to the heated palm kernel oil with
constant stirring to ensure complete mixing and reaction.
o Reaction Time: The mixture is allowed to react for several hours, with
continuous stirring, until saponification is complete.

2. Mixing and Additives

Objective: To incorporate additional ingredients into the soap to enhance its properties and
appearance.

Processes:

 Additives:
o Fragrances: Essential oils or synthetic fragrances are added for scent.
o Colorants: Natural or synthetic dyes are added to give the soap its color.
o Superfatting Agents: Extra oils (e.g., shea butter, coconut oil) are added to
increase the moisturizing properties.
o Preservatives: Added to prolong shelf life and prevent microbial growth.
o Other Functional Ingredients: Such as exfoliants (e.g., oatmeal, pumice) or
skin conditioners (e.g., aloe vera).
 Process:
o Cooling: After saponification, the mixture is cooled to a suitable temperature for
adding sensitive ingredients.
o Incorporation: Additives are mixed thoroughly into the soap base.

3. Molding
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
Objective: To shape the soap into bars or other desired forms.

Processes:

 Pouring: The soap mixture is poured into molds of various shapes and sizes.
 Shaping: The soap can be shaped into bars, blocks, or other forms using different types
of molds.

4. Curing

Objective: To allow the soap to harden and mature, improving its texture and longevity.

Processes:

 Initial Hardening: The soap is allowed to cool and solidify in the molds for 24-48
hours.
 Demolding: The solidified soap is removed from the molds.
 Curing Time: The soap bars are placed on racks or shelves to cure for 4-6 weeks. This
process allows excess water to evaporate, and the soap to become harder and milder.

5. Packaging

Objective: To prepare the soap for distribution and sale.

Processes:

 Cutting: Large blocks of soap are cut into individual bars if not already in final form.
 Stamping: Soap bars may be stamped with logos or other designs.
 Wrapping and Labeling: Each bar is wrapped in protective packaging and labeled
with necessary information such as ingredients, weight, and manufacturer details.

In summary, the production of soap from palm kernel oil involves the following steps:

1. Saponification: Palm kernel oil is mixed with an alkali (NaOH or KOH) to produce
soap and glycerol through the saponification reaction.
2. Mixing and Additives: Fragrances, colorants, superfatting agents, preservatives, and
other ingredients are incorporated into the soap mixture.
3. Molding: The soap mixture is poured into molds to shape it into bars or other desired
forms.
4. Curing: The soap is allowed to harden and mature for several weeks to improve its
texture and longevity.
5. Packaging: The soap is cut, stamped, wrapped, and labeled for distribution and sale.

This process results in high-quality soap that can be used for various personal and household
cleaning purposes.

THE MANUFACTURE OF DETERGENTS

The manufacture of detergents involves several chemical processes to produce cleaning agents
that effectively remove dirt and grease. The primary ingredients in detergents are surfactants,
which reduce surface tension and enhance the wetting and cleaning properties of water. Here
is a detailed description of the chemistry and processes involved in the manufacture of
detergents:
1. Raw Materials

Key Ingredients:

 Surfactants: These are the primary active ingredients in detergents.

o Anionic Surfactants: Sodium lauryl sulphate (SLS), sodium laureth sulphate
(SLES), linear alkylbenzene sulphonates (LABS) Page | 50
o Nonionic Surfactants: Ethoxylated alcohols, alkylphenol ethoxylates
o Cationic Surfactants: Quaternary ammonium compounds
o Amphoteric Surfactants: Cocamidopropyl betaine
 Builders: Enhance cleaning efficiency and soften water (e.g., sodium tripolyphosphate,
zeolites, sodium carbonate).

Builders are key ingredients in detergents that enhance their cleaning efficiency by
performing several important functions. These include softening water, increasing
alkalinity, stabilizing the surfactant system, and aiding in the removal of dirt and stains.
Builders help to maximize the performance of surfactants and improve the overall
effectiveness of the detergent. Here are the primary functions and types of builders used
in detergents:

Functions of Builders

1. Water Softening: Builders remove calcium and magnesium ions from hard
water, which can otherwise react with surfactants to form insoluble salts, reducing
their effectiveness. By binding these ions, builders prevent the formation of soap
scum and enhance the detergent's cleaning power.
2. Increasing Alkalinity: Builders maintain an optimal pH level (usually alkaline)
in the washing solution, which helps to break down acidic soils and stains, and
enhances the cleaning action of surfactants.
3. Stabilizing the Surfactant System: Builders prevent surfactants from being
deactivated by water hardness ions and other impurities, ensuring that they remain
active throughout the cleaning process.
4. Soil Suspension and Emulsification: Builders help to keep dirt particles
suspended in the wash water, preventing them from redepositing onto fabrics.
They also aid in emulsifying oily soils, making them easier to remove.

Types of Builders

1. Phosphate Builders:
o Sodium Tripolyphosphate (STPP): A widely used builder that
effectively softens water and enhances detergency. It has excellent
sequestering properties for calcium and magnesium ions.

3Ca2+ + 2Na5P3O10 → Ca3(P3O10)2 + 6Na+

2. Zeolites:
o Zeolite A (Sodium Aluminosilicate): An alternative to phosphates,
zeolites soften water by ion exchange, replacing calcium and magnesium
ions with sodium ions.

Ca2+ + Na2[Al2Si2O8] → Ca[Al2Si2O8] + 2Na+

3. Carbonates:
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
o Sodium Carbonate (Soda Ash): Increases alkalinity and precipitates
calcium and magnesium ions as insoluble carbonates.

Ca2+ + Na2CO3 → CaCO3 + 2Na+

4. Silicates:
o Sodium Silicate: Provides alkalinity, stabilizes emulsions, and inhibits
corrosion of metal parts in washing machines.

Na2SiO3 + Ca2+ → CaSiO3 + 2Na+

5. Organic Builders:
o Nitrilotriacetic Acid (NTA): A chelating agent that binds calcium and
magnesium ions, preventing them from interfering with surfactants.

Ca2+ + NTA → Ca-NTA

o Citric Acid: A biodegradable chelating agent that sequesters hardness ions

and provides alkalinity.

Ca2+ + Citric Acid → Ca-Citrate

In summary, builders are essential components in detergents that enhance their

cleaning efficiency by:

1. Softening Water: Removing calcium and magnesium ions to prevent

interference with surfactants.
2. Increasing Alkalinity: Maintaining an optimal pH level for effective cleaning.
3. Stabilizing Surfactants: Ensuring surfactants remain active throughout the
wash.
4. Suspending and Emulsifying Soils: Keeping dirt and oils suspended and
emulsified to prevent redeposition.

Common types of builders include phosphates (e.g., STPP), zeolites, carbonates,

silicates, and organic builders (e.g., NTA, citric acid). Each type of builder has
specific properties that contribute to the overall performance of the detergent.

 Fillers: Add bulk to the product (e.g., sodium sulfate).

 Bleaching Agents: Remove stains (e.g., sodium perborate, hydrogen peroxide).
 Enzymes: Break down proteins, starches, and fats (e.g., proteases, amylases, lipases).
 Additives: Fragrances, dyes, optical brighteners, preservatives.

2. Sulfonation

Objective:

To produce anionic surfactants through the sulfonation process.

Processes:

 Raw Material: Linear alkylbenzene (LAB) is the starting material.

 Sulfonation Reaction: LAB is reacted with sulfur trioxide (SO₃) to produce linear
alkylbenzene sulfonic acid (LABSA).
 C6H5CnH2n+1 + SO3 → C6H4CnH2n+1SO3H

 Neutralization: LABSA is then neutralized with sodium hydroxide (NaOH) to form

the sodium salt, which is the active surfactant.

C6H4CnH2n+1SO3H + NaOH → C6H4CnH2n+1SO3Na + H2O

Page | 52
3. Saponification

Objective:

To produce soap from fats and oils, which can be used as a surfactant in some detergents.

Processes:

 Raw Materials: Fats and oils (e.g., palm kernel oil, coconut oil).
 Saponification Reaction: Fats and oils are hydrolyzed with sodium hydroxide
(NaOH) to produce glycerol and soap (sodium salts of fatty acids).

Fat + NaOH → Glycerol + Soap

For example:

C3H5(COOR)3 + 3NaOH → C3H5(OH)3 + 3RCOONa

4. Ethoxylation

Objective:

To produce nonionic surfactants by reacting fatty alcohols or alkylphenols with ethylene

oxide.

Processes:

 Raw Materials: Fatty alcohols or alkylphenols.

 Ethoxylation Reaction: Fatty alcohols are reacted with ethylene oxide (EO) to
produce ethoxylated alcohols.

R-OH + nEO → R-(OCH2CH2)n-OH

Where n indicates the number of ethylene oxide units added.

5. Mixing and Blending

Objective: Combining all the ingredients to produce the final detergent product.

Processes:

 Batch Mixing: Ingredients are mixed in large batch reactors.

 Continuous Mixing: Ingredients are continuously fed into a mixer for large-scale
production.
 Addition of Additives: Fragrances, dyes, enzymes, and other additives are blended
into the mixture.
 ICH 453: INDUSTRIAL CHEMICAL PROCESSES II (2 CREDIT UNITS)
LECTURE NOTES
6. Drying and Granulation

Objective: To convert the detergent slurry into a solid form.

Processes:

 Spray Drying: The detergent slurry is sprayed into a hot air chamber, where water
evaporates, leaving behind fine detergent granules.
 Agglomeration: Detergent granules are agglomerated to produce larger particles,
improving solubility and handling properties.

7. Packaging

Objective: Packaging the detergent in suitable containers for distribution and sale.

Processes:

 Filling: Detergent powder or liquid is filled into bottles, boxes, or pouches.

 Sealing: Containers are sealed to prevent contamination and preserve product
quality.
 Labelling: Containers are labelled with product information, usage instructions, and
safety warnings.

In summary, the manufacture of detergents involves the following steps:

1. Sulfonation: Production of anionic surfactants by reacting LAB with SO₃ and

neutralizing with NaOH.
2. Saponification: Production of soap from fats and oils through hydrolysis with
NaOH.
3. Ethoxylation: Production of nonionic surfactants by reacting fatty alcohols with
ethylene oxide.
4. Mixing and Blending: Combining surfactants, builders, fillers, enzymes, and
additives to produce the detergent mixture.
5. Drying and Granulation: Converting the detergent mixture into a solid form
through spray drying or agglomeration.
6. Packaging: Packaging the final detergent product into suitable containers for
distribution and sale.

This process results in a variety of detergent products, including powders, liquids, and
tablets, designed for various cleaning applications.