A typical Industrial Process:

Unit Operations

Raw materials
Physical Chemical Physical
Products
treatment steps treatment steps treatment steps

pre-treatment • Separations
• Purifications
• Chemical Transformations
or Conversions

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Unit Processes 1
 Unit Operations
Unit operations is defined as physical transformations. They are many including
size reduction, size enlargement and separation of mixtures.

Basic unit operation

1. Conversion:
Thermochemical, Biochemical, Electrochemical, Photochemical, Plasma, Sonochemical

2. Separations:
Separation processes are used to:
• Purify raw materials.
• Purify products.
• Purify and separate unreacted feed.

Adsorption Systems are used in a natural gas

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Separation types
1. Solid-Solid separations
2. Liquid-Solid (Solid-
Liquid ) separators
3. Separation of dissolved
solids
4. Liquid- liquid separation
5. Separation of dissolved
liquids
6. Gas-Solid separations
(Gas cleaning)
7. Gas-Liquid separators
Other Unit Operations
Examples
Screening (sieving), Hydro separators and seizers, Hydraulic
jigs.
Filtration
Evaporatation, Crystallization
Decanters (settlers), Plate separators
➢Solvent extraction
Gravity settlers (settling chambers), Electrostatic precipitators
Vertical separators, Horizontal separators.
3
 Unit Operations
3. Mixing:
Component (Examples) Phase (Examples)
Gas-Liquid
Gas-Solid
Dissolving Liquid-Liquid
Liquid-Solid
Solid-Solid

4. Material Transfer:
• Pumping liquids.
• Compressing gases .
Schematics of an agitated vessel
• Conveying solids.

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 Unit Operations
5. Energy Transfer:
Expansion
Heat exchange

6. Storage:
Raw materials, Products

7. Size reduction:
8. Agglomeration:
9. Size separation:
Industrial oil tanks in a refinery

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 Other Unit Operations
Unit Operation Purpose Application
Electrostatic Separation of solids on the basis of the difference Mineral ore dressing
separation in electrical conductivity of components
Sedimentation Separation of solids from liquids mostly by Water treatment plants
gravitational forces
Crystallization Separation of solid particles from their saturated Sugar manufacture
solutions
Solid–liquid Extraction of a soluble solid from its mixture with an Mineral ore processing
extraction or inert solid, by use of liquid solvent in which it is
leaching soluble.
Spray drying A liquid containing a dissolved solid is sprayed and Production of pigments, detergent
contacted with hot air which evaporates the solvent powder, powdered milk, synthetic
yielding a powdered product. resins and inorganic salts.

Liquid – liquid or Separation of a liquid solute from its mixture with Solvent recovery, removal of
solvent extraction another ‘’inert’ liquid by means of another liquid in naphthenic and aromatic
which it is soluble. compounds from lubricating oil
Absorption Removal of a component from a gas mixture by Removal of hydrogen sulphide
dissolving it in a liquid. (H2S) from hydrocarbon gases
using alkaline solutions. 6
 A typical Industrial Process:

Unit Operations

Raw materials
Physical Chemical Physical
Products
treatment steps treatment steps treatment steps

pre-treatment • Separations
• Purifications
• Chemical Transformations
or Conversions

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Unit Processes 7
 Unit Process (Chemical Process)
• A chemical process is any single or a combination of processing units used for
the conversion of raw materials through any combination of chemical and
physical treatment changes into finished products.

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 Unit process
Examples of unit processes
• Acylation is the process of adding an acyl group (ArCO-) to a compound.
• Calcination is the heating to high temperature in air or O2.
• Dehydrogenation is a chemical reaction that involves the removal of
hydrogen H2 from an organic compound.
• Hydrolysis is the chemical breakdown of a compound due to reaction with
water.
• Alcoholysis (Transesterification) is the displacement of alcohol from an
ester by another alcohol.
• Carboxylation is a chemical reaction in which a carboxylic acid group is
produced by treating a substrate with CO2. The opposite reaction is
decarboxylation.
• Decomposition is the process by which organic substances are broken
down into simpler organic matter.
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• Ion exchange is an exchange of ions between two electrolytes or between an
electrolyte solution and a complex.
• Alkylation is the transfer of an alkyl group (R- ) from one molecule to another.
• Electrolysis is a technique that uses a direct electric current to drive a non-
spontaneous chemical reaction.
• Isomerization is the process by which one molecule is transformed into another
molecule which has exactly the same atoms, but the atoms have a different
arrangement e.g. A-B-C to B-A-C.
• Amination is the process by which an amine group (NH2- ) is introduced into an
organic molecule.
• Combustion is the rapid chemical combination of a substance with O2, involving
the production of heat and light.
• Esterification is a chemical reaction that occurs between the carboxylic acid and
the alcohol where esters are obtained.
• Neutralization is a chemical reaction in which an acid and a base react
quantitatively with each other.
• Ammonolysis is any chemical compound reacts with a molecule of ammonia or
an amine and causes molecules to split into two parts, containing the addition of
an amine group (-NH- ).
• Condensation is the conversion of a vapor or gas to a liquid.
• Fermentation is a metabolic process in which an organism converts a
carbohydrate into an alcohol or an acid.
• Oxidation is the process of being oxidized.
• Aromatization is a chemical reaction in which an aromatic system is formed from
a single non-aromatic precursor.
• Dehydration is the removal of H2O from a molecule.
• Hydrogenation is a chemical reaction between molecular hydrogen H2 and
another compound or element in the presence of a catalyst such as nickel.
• Pyrolysis is the decomposition brought about by high temperatures.
 Polymerization and Esterification
• Polymerization is one of the very important unit processes which find
application in manufacture of polymer, synthetic fibre, synthetic rubber,
polyurethane, paint and petroleum industry for high octane gasoline.

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 Preparation of Saccharin
The industrial synthesis entails the reaction of hydrogen chloride with a solution
of sulfur trioxide in sulfuric acid. Sulfonation by chlorosulfonic acid gives the
ortho and para substituted chlorosulfones. The ortho isomer is separated and
converted to the sulfonamide with ammonia. Oxidation of the methyl substituent
gives the carboxylic acid, which cyclicizes to give saccharin.

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 Flow sheets (Flow Diagram)
• It is a diagrammatic model of the process, which is used to describe the
operating details of chemical processes.
• The flow-sheet will be used by the specialist design groups as the basis for
their designs. This will include piping, instrumentation, equipment design
and plant layout.

14
 Classification of Flow Diagrams

➢Block Flow Diagrams (BFD)

➢Process Flow Diagrams (PFD)
➢Piping and Instrument Diagrams (P&ID)
➢3-D plant layout diagrams

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 1. Block Flow Diagrams (BFD)
• This is a schematic diagram, which shows:
• What is to be done rather than how it is to be done.
• Details of unit operations/ processes are not given.
• flow by means of lines and arrows.
• unit operations and processes by figures such as rectangles and
circles.
• raw materials, intermediate and final products.

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 An example of a block diagram (Block diagram of an ammonia plant)

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 (Block diagram for the production of Benzene)

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 2. Process flow diagram/ flow sheet
A process flowsheet is a collection of icons to represent process units and
arrows to represent the flow of materials to and from the units.

Fresh feed

Distillation
tower
Reactor

steam Furnace
Flash
Product

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Below is a cement process flow diagram illustrating the use of equipment
symbols.

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 3. Piping and Instrumentation Diagram (P&ID)

It is shown as a comprehensive
diagram that includes additional
details such as pipe sizes, utility
streams, sample taps, numerous
indicators, and so on. It is the only
unit operation on the diagram.

Piping and Instrumentation Diagram for Benzene Distillation

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4.
3-D Plant
Diagrams

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 Water Pollution
• Water pollution is the contamination of water bodies (e.g. lakes, rivers,
oceans, and groundwater), very often by human activities.

• Any change or modification in the physical, chemical and biological

properties of water, which will have a detrimental consequence on living
things, is water pollution.

• Water pollution is the second most imperative environmental concern

along with air pollution.

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 Types of water pollution
1. Nutrients Pollution
Some wastewater, fertilizers and sewage contain high levels of nutrients. If they
end up in water bodies, they encourage algae and weed growth in the water.
2. Surface water pollution
Hazardous substances coming into contact with the surface water, dissolving or
mixing physically with the water can be called surface water pollution.
3. Oxygen Depleting
If oxygen is depleted, aerobic organisms die, and anaerobic organisms grow more
to produce harmful toxins such as ammonia and sulphides.

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 Types of water pollution
4. Ground water pollution
When humans apply pesticides and chemicals to soils, they are washed deep into the
ground by rainwater. This gets to underground water, causing pollution underground.

5. Microbiological
Sometimes there is natural pollution caused by microorganisms like viruses, bacteria and
protozoa. This natural pollution can cause fishes and other water life to die. They can also
cause serious illness to humans who drink from such waters.

6. Suspended Matter
Some pollutants (substances, particles and chemicals) do not easily dissolve in water.
This can harm and even kill aquatic organisms that live at the bottom of water bodies.

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 Types of water pollution
7. Chemical Water Pollution
Many industries and farmers work with chemicals that end up in water. These are
poisonous to many forms of aquatic life and may slow their development, make them
infertile and kill them.

8. Oil Spillage
Oil spills usually have only a localized effect on wildlife but can spread for miles. The oil
can cause death to many fish and get stuck to the feathers of seabirds causing them to
lose their ability to fly.

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 Types of water pollution

Other causes of water pollution:

• Sewage and waste water

• Septic Tanks

• Ocean and marine dumping

• Underground storage and tube leakages

• Atmospheric

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 Chemical tests of water quality
• Turbidity
• Specific Conductivity/TDS
• pH
• Temperature
• Alkalinity/Hardness
• Nitrites/Nitrates/Ammonia
• Phosphates
• Dissolved Oxygen
• Arsenic
• Fluoride
• Bacteria
• Others
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 EPA National Drinking Water Standards

Specific Conductivity/TDS 500 mg/L

pH 6.5-8.5
Nitrates/Nitrites 10mg/L as N, 1 mg/L as N
Turbidity 5 NTU
Color 15 color units
Arsenic 0.010 mg/L
Fluoride 4.0 mg/L
Sulfate 250 mg/L
Chloride 250 mg/L
Bacteria public health goal = 0

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 Hardness of water
• The presence of dissolved mineral matter in water results in hardness and
alkalinity.

• When water passes through or over deposits such as limestone, the levels of
Ca2+, Mg2+, and HCO-3 ions present in the water can greatly increase and
cause the water to be classified as hard water.

Total Hardness Unit (mg/L)

as Ca(HCO3)
Soft 0-30

Moderately soft 30-60

Moderately hard 60-120

Hard 120-180
Very hard >180
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• Hardness caused by dissolved calcium and magnesium salts:
➢ Calcium sulphate - CaSO4, magnesium sulphate - MgSO4
➢ Calcium chloride - CaCl2, magnesium chloride - MgCl2
➢ Calcium hydrogencarbonate - Ca(HCO3)2, magnesium- Mg(HCO3)2

• Hardness of water is commonly defined as its soap-consuming capacity.

Generally, soaps consist of sodium salts of higher fatty acids such as oleic,
palmitic and stearic acids. Consumption of soap by water is mainly due to the
presence of dissolved calcium and magnesium ions. A typical reaction can be
represented as follows:

2C17H35COONa + CaCl2 → (C17H35COO)2Ca + 2NaCl

Soap(soluble) calcium soap
(insoluble)
Types of Water Hardness

Hard water contains dissolved magnesium and calcium ions.

These make it more difficult for the water to form a lather with
soap.

A. Temporary Hardness:
Temporary hardness is caused by dissolved calcium and
magnesium hydrogencarbonate Ca(HCO3)2 and Mg(HCO3)2
(which is removed by boiling). Permanent hardness is caused by
dissolved calcium and magnesium sulfate and chloride (which is
not removed by boiling).
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 Types of Water Hardness
A. Temporary Hardness:
The Ca2+ ions cause hardness while the HCO3- ions have no effect. However, if water
containing these two ions is heated the water is softened as a chemical reaction occurs
which removes the Ca2+ ions from the water:

Heat
Ca(HCO3)2 → CaCO3↓ + CO2 + H2O
Soluble Insoluble

The insoluble calcium carbonate precipitate

can form a fur/scale that builds up on kettles,
boilers, hot water pipes etc. The build up of
this lime scale can cause problems such as
wasting heat, or even explosions due to
pipes being completely clogged.
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 Types of Hardness

B. Permanent Hardness:
Permanent hardness is hardness in water that can only be removed by methods
other than boiling i.e. ion exchange, distillation.
Caused by:
- sulphates of calcium (gypsum rock) and magnesium
- chlorides of calcium and magnesium

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 Methods of removing hardness (permanent & temporary) from water:

A. Distillation:
➢ Involves boiling the water and then cooling the vapour
➢ All dissolved and suspended solids and dissolved liquids are removed from
the water.
➢ Very pure water
➢ Not used on a large scale to soften water due to the expense involved in
boiling the water.

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 Methods of removing hardness (permanent & temporary) from water:

B. Washing Soda: (Hydrated Sodium Carbonate – Na2CO3.10H2O )

Before the development of modern detergents clothes were washed with soap
and crystals of this compound were added to the water to soften the water.

➢ Carbonate ions in the washing soda react with Ca2+ ions in the water and
removes them as insoluble calcium carbonate:

Ca2+ + CO32- → CaCO3↓

➢ Na+ ions (sodium carbonate) remain dissolved in water

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 Methods of removing hardness (permanent & temporary) from water:

B. Ion Exchange Resin/ Deionisation (Swap Shop):

• Modern ion exchange resins are man-made materials, which exchange ions
that cause hardness (Ca2+, Mg2+) with ions that do not cause hardness (Na+).
• Ion exchange units used to soften water contain cation (positive ion)
exchange resin.
• The resins used are complex sodium compounds and may be represented as
RNa.
• The Ca2+ and Mg2+ ions in the hard water swap places with the Na+ ions in the resin:

2RNa(s) + Ca2+(aq) → R2Ca(s) + 2Na+(aq)

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Ion Exchange Resin
 Stages of Wastewater Treatment:
1. Screening (Sieving).
2. Flocculation.
3. Settlement (Sedimentation).
4. Filtration.
5. Chlorination.
6. Fluoridation.
7. pH adjustment.

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 Stages of Wastewater Treatment:
1. Screening:
Water is first passed through a wire mesh to remove any floating debris –
twigs, plastic bags, …etc.

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 Stages of Wastewater Treatment:
2. Flocculation:
• Flocculation is the coming together of small suspended solids in water to form
larger particles (flocs)
• This is done by adding certain chemicals (flocculants) to the water –flocculating
agent such as Al2(SO4)3
Al2(SO4)3 + 3Ca(HCO3)2 → 2Al(OH)3 + 3CaSO4 + 6CO2
Present in water flocculent ppt.

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 Stages of Wastewater Treatment:
3. Settlement (Sedimentation):
• The flocculated water is pumped into the bottom of large settlement tanks
and rises up slowly (allows maximum settlement to take place at bottom of
tank) to the surface where clear water is collected in channels.

• The suspended particles settle to the bottom and approximately 90% of

particles are removed in settlement stage.

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 Stages of Wastewater Treatment:
4. Filtration:
• The water, from top of settlement tanks, is allowed to fall through beds of graded
sand and gravel.
• These filter beds remove any remaining suspended solids.
• The sand acts just like a sieve or filter paper in removing the suspended solids.
• The water coming out of filter beds is now clear but not yet fit for human
consumption.

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 Stages of Wastewater Treatment:
5. Chlorination
• Chlorine is added to water in order to sterilise it i.e. kill any harmful micro-
organisms.

• Chlorine may be added as elemental chlorine or more commonly in the

form of sodium hypochlorite (NaOCl).

• Chlorine requirements in drinking water 0.2-0.5ppm

• Chlorine requirements in swimming pool water 1-5ppm

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Chlorination
 Stages of Wastewater Treatment:

6. Fluoridation:
• Involves adding small quantities (1ppm) of fluorine compounds to water

• Fluoridation of water is carried out because it has been shown that the
presence of fluoride ions in water can help prevent tooth decay – strengthens
enamel of teeth
• Sources of fluoride ions:
➢Sodium fluoride, NaF
➢Hexafluorosilicic acid, H2SiF6

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 Stages of Wastewater Treatment:

6. pH Adjustment:

• It may be necessary to adjust the pH of water before it leaves treatment plant

• Optimum pH of water for distribution (pH 7-9)

• If water supply slightly acidic (due to original source or chemicals added) can

lead to corrosion of pipes so calcium hydroxide (lime) added to raise pH above 7

• If water supply slightly basic (due to added softeners-sodium carbonate)

sulphuric acid added to lower pH.

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pH Adjustment
Determination of Hardness of Water by EDTA Titration:
The ions involved in water hardness, i.e. Ca2+(aq) and Mg2+(aq),
can be determined by titration with a chelating agent,
ethylenediaminetetraacetic acid (EDTA), usually in the form of
disodium salt (H2Y2-). The titration reaction is:
Ca2+(aq) + H2Y2-(aq) ⎯⎯→ CaY2-(aq) + 2H+(aq)

EDTA (anionic form)

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Eriochrome Black T is commonly used as indicator for the above
titration. At pH 10, Ca2+(aq) ion first complexes with the indicator
as CaIn+(aq) which is wine red. As the stronger ligand EDTA is
added, the CaIn+(aq) complex is replaced by the CaY2-(aq) complex
which is blue. The end point of titration is indicated by a sharp
color change from wine red to blue.

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Experimental Procedures

Determination of total hardness:

1. Pipette 50 cm3 mineral water into a conical flask.
2. Add 2 cm3 buffer solution followed by 3 drops of Eriochrome
Black T indicator solution.
3. Titrate with 0.01 M EDTA until the solution turns from wine red
to sky blue with no hint of red.
4. Repeat the titration to obtain two concordant results.
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Calculation:
At the end point number of moles of EDTA will be equal to number
of moles of CaCO3:
mole = M x V
moles of CaCO3 = (M x V) of EDTA = 0.01 x 10/1000 = 0.0001 mole
Wt. CaCO3 = mole x M.Wt. = 0.0001 x 100.1 = 0.01 g = 10 mg
The concentration of CaCO3 in the water sample = 10 mg/50 ml
The concentration of CaCO3 in ppm = 200 mg/L

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Example :
A 100 cm3 of mineral water sample was titrated with
5 cm3 of 0.01 M EDTA solution.
Calculate total hardness for the water sample.