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Chemical Processing, Unit Operation &

Unit Process
Chemical Process Selection, Design and Operation

Adequate and flexible initial design is essential for the promotion of

a chemical plant organic product or inorganic product.

In older days it was classified as inorganic chemical technology and

organic chemical technology. Subsequently the oxford university
made it as chemical works organization and management.

Some factors that must be considered in planning a plant are

discussed in this section. The Process Engineer is an expert in the
current aspects of chemical process design. Practical experience is a
must if the senior design engineer is able to foresee and solve the
problems of production, such as maintenance, safety and obeying
the government, environmental by loss and control.
Experience consultants either individuals or professional consulting
firms are able to advise, design and for erection of chemical plants.
Chemical Process Control and Instrumentation

Automatic and Instrument control chemical processes are common

and essential. Instruments should not be chosen simply to record a
variables, of the process. But their function is to assure consistent
quality by sensing controls, recording and maintaining desired
operating conditions. Instruments are the essential tool for modern
processes. They are classified as
1. Indicating Instruments
2. Recording
Instruments
3. Controlling Instruments

Two types of Instruments are currently used as analogue and

digital.

Analogue Instruments such as pressure spring thermometers and

Bourden Gauges shows results by mechanical moments of some
type of device which is directly proportional to the quantity
measured.

On the other hand, digital devices are converts the quantity

measured into a signal and electric circuits converts the signal to
read the numerical values forward by control. Now the computers
can monitor and regulate outputs from both the analogue and
digital devices according to a prearranged program, also general
conventional digital inputs are required. Chemical analytical control
has been used in day to day factory procedures for analysis of
incoming raw material or outgoing products. Thus quality chemicals
are produced more in these days reliably their when human
analysed control were used.

The latest advancement are the chromatography system, many

spectroscopy have been automated an install of on-line basis for the

process to run continuously without the problems encountered

manually before.
Role of Chemical Engineers

Chemical Engineers are trained primarily to work in chemical

industries. some of the vital role of the chemical engineers are as
follows;
Chemical Process Economics

Engineer are totally different from Scientist by their customers of

cost of production and profit generator. Therefore the objective of
engineer should be to deliver safely the best product or most
efficient service at lower cost to the employer and the public who
consumes the product.
Material Balance

Yield and conversion are the chemical prospects from the basis for
the material balances which is useful for cost determination.

Materials and their quantities from the standard practices are

tabulated in the flow charts, energy given are observed for the
chemical reactions and energy is frequently a major cost in chemical
plants but it often possible by altering the process procedures by
using modern separation technologies like RO and Advanced
Separation Processes to produce high quality chemicals with low
energy consumption.
Plant Location

The location of the chemical plant is decided ourselves by the

availability of raw materials, transportation, market and power. Now
the environmental constituents, water supply, availability of efficient
labor, cost of land and waste disposal facilities form the criteria for
the plant location.
Construction of Plant

For small and large companies construction engineering

organizations are available that will built a plant and participate in
its design. Some large chemical companies have their own civil
construction department and starts their own plants.

The advancement of this is the worker who is going to operate the

equipment can be more intimately corrected to the constructions
and be familiar themselves for the future alternatives, expansion or
modifications.

In built-in plants the top engineers are chartered engineers qualified

for the development activities. They have been trained and suitably
examined to guarantee technical competency and owe personal
responsibility. They are now called as functional consultants and
registered firm for dealing with legal aspects with proper training.
Research and Development

adequate and skilled research with patent protection is necessary

for future profits. In the chemical process industries one of the
outstanding tactics is rapidly changing processes, new raw materials
and new markets. Research creates these changes and the factory
will have a competitive progress. This research brings about

development and the adoption of ideas, concepts, methodologies

form the production of the industry. The results and benefits of
research establishes the developing coutry on the road of progress
and raise the level of life of common man.
Chemical Engineer in coming years

1. Resources particularly energy and feed back for the Fertilizers

and Heavy Chemical Industries.
2. Infrastructure for Transportation and Telecommunications.
3. Protection of the Environment.
4. Development of Agro Industries where utilization of waste
from Agro industries and exploitation of value added products
from wastes.
5. Transformation of Rural Economy, Industrialization and
Privatization where the profits are less and consumption is
more.
6. Problems of less Technical context are,
The Centre Vs. States
Command Economy Vs. Liberalisation & Privatisation
Internal Budget and External Balances
World Trade Globalization and relevant to India
Problem of Indian competitiveness

The latest research and development have classified the following

new industries;
1.
2.
3.
4.
5.

6.
7.
8.
9.
10.
11.
12.

Cryogenics in Chemical Technology

Chemicals from Sea
Air as a Chemical Raw Material
NUPLEXES ( Nuclear Power Agro Industrial Complexes )
Proteins from Petroleum Fermentation and Single Cell Proteins
from Animal horns.
Food Industries
Coal Chemicals
Newer Petrochemicals
Pesticides
Pharmaceuticals Industries
Metallurgical Industries
Water treatment & Air Pollution Control

The chemical process industry had its growth from pre scientific
chemical industries followed by scientific chemical industry. The
growth with restrains, green challenge to chemical industry and the
modern separations process involved in the indian chemical industry
seen today.
We define Chemical Engineering as a synthesis of chemistry and
engineering. A Chemical Engineering therefore carries out on a large
scale reactions developed in the laboratory by the chemist.
The Major Areas of Work within Chemical Engineering are,

Research
Process Development
Process Design
Evaluation of Design
Plant Design
Construction

 Production Supervision
Plant Technical Services
Sales of the Product

The Research is divided into three categories like Fundamental

Research, Exploratory Research and Process Research.
S.No.

Industry

Inorganic
Chemicals

Organic
Chemicals

Petroleum&
Petrochemicals

Typical Products

End User

H2SO4

Fertilizers,
Chemicals,
Petroleum
Refining, Paints,
Pigments, Metal
Processing and
Explosives

HNO3

Explosives &
Fertilizers

NaOH

Rayon, Film
Processing,
Petroleum
Refining, Pulp &
Paper Industry,
Lye, Cleaners,
Soap &
Detergents,
Metal Processing

Acetic Anhydride

Resins, Plastics &

Nylon

Ethyl Alcohol

Antifreeze
agents,
Cellophane,
Dynamite & Syn.
Fibres

Formaldehyde

Plastics

Methanol

Mfr. Of
Formaldehyde,
IMS(Industrial
Methylated
Solvent) &
Antifreeze agent

Gasoline

Motor Fuels

Pulp & Paper

Pigments &
Paints

Kerosene

Fuel

Oil

Lubrication &
Heading
purposes

Ammonia

Fertilizer &
Chemicals

Ethanol

Acetaldehyde
solvents & other
miscellaneous
chemicals

Alkyl Aryl
Sulfonate

Detergents

Styrene

Syn. Rubber,
Polymers &
Plastics

Paper

Books, Records &

Newspaper

Cardboard

Boxes for
packing

Fiber Board

Building
materials

Zinc Oxide (ZnO)

Pigments for
paints, inks,
plastic, rubber,
ceramics and
linoleum

TiO2
Carbon Blade

Drying Oil

Lead Chromate
Linseed Oil
Phenolic Resins

Basic kequer
warmish &
enamels

Alkyl Resins

Ion exchange
resins and
constituents of
enamel

Rubber

Natural Rubber
(Isoprene)
Syn. Rubber
(Neoprene)

Automobile tyres,
moulds, sheets,
footwear and
insulation

Butyl Rubber
7

Plastics

Phenol
Formaldehyde
Poly Styrene

Various users in
all areas of
everyday life

Polymethyl
methacrylate
PVC
Polyethylene
Polyster
8

Synthetic Fibers

Rayon

Clothing

Nylon
Acrylics
Polyster
9

10

Minerals

Cleansing
Agents

Glass & Ceramics

Windows,
containers, bricks
& pipe tubes

Cement

Concrete for
construction of
buildings,
highways, etc.

Coal

Fuels, coke and

its by-products

Soaps &
Detergents

House hold
cleaning &
Industrial
cleaning. Sodium
alkyl aryl
sulfonate is also
used as wetting
agent.

11

12

Bio Chemicals

Metals

Pharmaceuticals &
Drugs

Health &
Medicine
applications

Fermentation
product like
penicillin

Medical use

Ethyl Alcohol

Solvent and
Beverages

Food Products

Human sustance

Steel, Cu, Al &

Zirconium

All the Building

materials,
machinery etc.

Uranium

Nuclear fuel

The largest tonnage inorganic chemicals is H2SO4. It is consumed by

industry in the manufacture of other products. Thereby it reaches
the public knowledge vary scarely. Large quantities are consumed
by petroleum and metal industries. The important organic chemical
include alcohols, dyes, dye intermediates used to produce other
chemicals. Ethyl alcohol was initially produced by bio chemical
fermentation before the second world war.
But now it is produced primarily from petroleum on the latest
discovery of natural gas. The important petroleum products are
gasoline, lubricants, petrochemicals, other fuels and miscellaneous
chemicals. Since the second world war petrochemicals have
assumed a commander role in the economy. The largest
petrochemical ammonia is produced by reaction of H2 from natural
gas or petroleum with N2 available in the Air.
This Ammonia reacts with CO2 to produce Urea in a fertilizer plant.
Normally there are five different units in the fertilizer manufacture
from coal based mines.
1.
2.
3.
4.
5.

Oil & Gasification plant

Benfield De-sulphurization plant
Ammonia plant
CO2 plant
Urea plant

The tendency of Urea is to form BIURETS which are used as

regenerator salts in the metallurgical applications. Many plastics and
synthetic detergents are produced with the help of oil refineries.
Unit Operation

The basic physical operations of chemical engineering in a chemical

process plant, that is distillation, fluid transportation, heat and mass
transfer, evaporation, extraction, drying, crystallization, filtration,

mixing, size separation, crushing and grinding, and conveying. In

simple terms, the operation which involves physical changes are
known as Unit Operation.

1. Distillation is a unit operation is used to purify or separate

alcohol in the brewery industry.
2. The same distillation
petroleum industries.

separates

the

hydrocarbon

in

3. Dry grapes and other food products or similar drying of filter

precipitate like rayon industry where yarn is produced.

4. Absorption of oxygen from air in a fermentation process of a

sewage treatment plant and half hydrogen gas in a process fr
liquid hydrogenation of oil.
5. Evaporation of salts solutions similar to evaporation of sugar
solution in the industry.
6. Settling and sedimentation of suspend solids similar to
minimizing and sewage treatment plant.

7. Flow of liquid hydrocarbon in a petroleum refinery and flow of

milk in a daily plant for the solidification in spray dryer.
Classification of Unit Operations

1. Fluid Flow : Concerns the principle that determine the flow

or transformation of fluids from one point to another. The fluid
can be a liquid or a gas. This unit is entirely based on
Bernoulli e's equation followed by continuity correlation.
2. Heat Transfer : Deals with principles that govern
accumulation and transfer of heat and energy from one place
to another. The three concepts followed here are conduction,
convection and radiation.
3. Evaporation : A special case of heat transfer which deals
with the evaporation of volatile solvent such as waste from a
non-volatile solute such as salt or any other material in the
solution. The evaporation of trichloro-ethylene a cleaning
agent in the automobile service industry and acetone in the
case of glassware in a chemical process industries follow this
unit operations.
4. Drying : An operation in which volatile liquids (usually water)
are removed from solid material.
5. Distillation : An operation where a components of the liquid
mixture are separated by boiling because of their difference in
vapor pressure.
6. Absorption : A process whereby a component is removed
from gas mixture by treatment with liquid.
7. Liq-Liq Extraction : A process in which a solute in a liquid
solution is removed by contact with another liquid solvent that
is relatively irreversible with solution.
8. Liq-Solid Leaching: It involves treating a finely divided solid
with a liquid that dissolves and removes a solute contain in
the solid.
9. Crystallization : The removal of a solute such as a salt from
solution by precipitation in the industries for large scale

operations, electrostatic precipitation is operated for this

concept.
10. Mechanical physical separation: This involves separation
of solids, liquids or gases by mechanical means such as
filtration, settling, size reduction which are classified as
separate unit operations.
The outline of unit operation defines the settling tanks
for sedimentation, filter press for separations,
pressurized spheres for ammonia storage, pellatising for
fertilizer compounds, pneumatic conveyors for cement
industry, bucket wheel elevators for thermal power
stations and belt conveyors for core industries and
many more in operation.

Stacks

Gases are discharged into the ambient atmosphere by stacks

(referred to as chimneys in industry) of several types.
The chemical process steps involved the following;
1.
2.
3.
4.

Preparing the Reactors

React them
Separate the Products
Purify the Products

The purpose of chemical industry is to start from one and other

chemical raw material arrive at a consumer product through a group
of physical and chemical products. Therefore it is called as a
creative industry rather than assembly industry.
This mainly fall into inorganic, natural products, organic chemicals
and metallurgical industry.
Unit Processes

Processes that involve making chemical changes to materials, as a

result of chemical reaction taking place. For instance, in the
combustion of coal, the entering and leaving materials are differ
from each other chemically. Coal and Air enters, and flue gases and
residues leave the combustion chamber. Combustion is therefore a
unit process. Unit processes are also referred to as chemical
conversions. In simple terms, the process which involves chemical
changes are known as Unit Processes.

Together with unit operations (physical conversions), unit processes

(chemical conversions) form the basic building blocks of a chemical
manufacturing process. Most chemical processes consist of a
combination of various unit operations and unit processes.
1. Alkylation:

Addition of alkyl radical (CH3) with side chain final product.

This alkylation process is widely used in organic chemicals and
petroleum industries. The reaction is given as,
C=C-C-C + C-C-C
2. Amination by Ammonolysis:

Cl-CH2CH2Cl + 4NH3 ------->NH2CH2CH2NH2

EDC
Ethylene Diamine

This reaction is used in manufacture of dye stuffs, organic

chemicals and synthetic fibres.
3. Amination by Reduction:

CH3CHNO2CH3 + 3H2 ------> CH3CHNH2CH3

2 Nitro Paraffin
Iso Propylamine

This unit process is also used in the manufacture of dye

stuffs and organic chemicals.
4. Amino Oxidation:

CH3CH2CH3 + NH3 + 1.5 O2 -----> CH2:CHCN + H20

Propylene
Acrylonitrile

This reaction is used in the manufacture of plastics and

synthetic fibres.
5. Calcination:

CaCO3 -----> CaO + CO2

Limestone
Lime
Heat

This reaction is used in the cement industry.

6. Carbonylation:

CH3OH + CO -----> CH3COOH

Methanol
Acetic Acid
This is used in the manufacture of organic chemicals.

7. Carboxylation:

This reaction is used in the organic chemical industry.

8. Combustion:

CH4 + O2 ------> CO2 + 2H2O

( Process Heating )

9. Condensation:

C6H5CHO + CH3CHO ------> C6H5CH:CHCHO + H2O

Benzaldehyde+Acetaldehyde
Cinnamaldehyde

10.Cracking or Pyrolysis:

C-C-C-C-C-C-C --------> C-C-C + C=C-C-C

This reaction is used in petroleum destruction and

distillation of coal.
1. Fluid - Solid Contact:

Represented by fixed bed reaction. It is most widely used in

catalytic reactor used with precious metal catalyst
to minimize attrition losses. The catalyst used in the form of pellets.
It can represented by the following figure.

This is used in the packed column. The design of the column is

determined by the breakthrough curve, equilibrium line for the
given system of adsorbent and adsorbate's. The volume of the
reactant coming from the top and the volume of which the product
leaves the column, residence time, distribution decides
the dimensions of the column. It is contrary to the fluid bed reactor
where the bed is fluidized. Once the minimum fluidized velocity is
reached the porosity of the bed is faster in a fixed bed reactor but
varies from the fluidized bed where the porosity changes according
to the height of the bed.
2. Fluid - Solid Separation: (Centrifugation)

This operation separates very finely divided solids from liquid or

mixture of liquid and liquid emulsion.

3. Wet Scrubber:

It is an effective means of removing suspended particles from

gas string by contact with liquid shower.

When solids are used in the place of liquid the operation is called
Dry Scrubber. In the manufacture of MEK, wet scrubber is used and
in other selected process industries Dry Scrubbers are used,
Scrubber just washes away the impurities and separate the
product for further purification.
4. Filter Press:

It is the simplest type of pressure filtration. the two important

parts of the filter press are plates & frames and fabric used in
between the two are made of variety of corrosion resistant
materials. In the laboratory scales asbestos cloth are used for
filtration at different pressures.
The operation decides the value of specific cake resistance, filter
medium resistance and compressibility of the chemical namely
Kieselghur a specific compound in the nature of diatomacceous
earth which are used in the application of bio-physics and
cyrstallography.

5. Fluid Storage:

Tanks are widely used for storage of liquids of all types and
atmospheric pressure when the liquid is highly volatile there is a
floating roof which acts as lid for chemicals as and when the vapour
pressure at which signifying the boiling point of liquid the roof

changes its position and deserves the liquid from going out to the
atmosphere.

6. Pressurized Spheres:

Pressurized spheres are used for pressurized storage

of liquefied gases or high vapors. The pressure permits safe storage
with no vapor losses. This is seen in the fertilizer plant where
ammonia is stored in spheres.

7. Gas-Liquid Contact: (Absorption)

The best example is Absorption. It is used for taking a soluble gas

in a solvent liquid and producing a solution plus an exit gas.
Hydrogen Sulphide is removed from hydrocarbon by
the absorption process.

8. Adsorption:

It is classified into physiorption and chemisorption according to

the process applied. The former one is almost a physical change or
physical transformation while a later represents a chemical reaction
which is a irreversible one. the common effluent treatment plants of
varies nature lied textile effluents, sewage treatment, ETP plants in
chemical industry, removal of hazardous solid wastes, etc are dealt
with adsorption method and the adsorbent is regenerated over a
period of time and used again and again.
9. Heat Exchangers:

The various cooling towers of natural draft and forced draft are
example of industrially applied H.Es. These are common facilities in
the thermal power stations and in chemical industries the
application of shell & tube heat exchangers are widely used. this is
an excellent application of heat transfer from one medium to the
other.
10.Membrane Separation:

Dialysis is used to separate metals in solution having widely

different molecular weight. for example caustic from sugar solution
or cellulose.
11.Size Reduction:

This involves crushing, grinding, pelletizing and prilling. Pelletizing

is used in pharmaceutical industries and prilling used the
manufacture of Urea.
Modern chemical processes are offer extremely complex operations
involving 100s of pieces of equipment. without a systematic
approach it would be impossible to analyses an existing process or
to design equipment process. The typical chemical process
is analyzed with the following interdependent considerations like,
-

Mass & Energy Balance

Thermo chemistry
Unit Operations
Plant Equipment
Ancillary Equipment
Process Plant Diagram
Instrumentation Control
Economics
which deals with net profit before taxation profit after
taxation dividend paid to the public and share holders. Once the
process as been developed and completed attention can be made to
access the various liabilities, resource and assets.
Alternatives and the remaining choices can be ranked in the order
of desirability. They are as follows;
- Effectiveness for reducing waste
- Technical Risk

- Extended of current views in the facility

- Industrial Precedent
- Capital and Operating cost incurred
- Effect of the Quality of the product
- Impact of Plant Operations
- Required time for Implementation
- Other aspects important in the particular situation according to
the industrial
Conservation of Energy:
dE = Q - W
dH = Q - Ws

This is a steady state batch process.

Thia is for flow process.

Q--> Heat energy transfered across system boundary.

W-->Work energy transfered across system boundary.
Ws->Mechanical work energy transfered across system
boundary.
E--> Internal energy of the system.
dE, dH--> Changes in Internal Energy & Enthalpy during the
process.
we are already classified the various unit operations and below is a
particular basic column of mass transfer equipment.

1. Distillation:

It is classified into Batch and Continuous Fractionation.

a. Batch Fractionation:

Used for intermittent operation and handling of small volume

of feed and products.
b. Continuous Fractionation:

These are used for high volume continous seperation of

complex mistures such as petroleum fractions connected to
appropriate pumps, re-boilers, condensers, scrubbers, strippers and
finally automatic controls.
2. Drying of Solids:

Spray Dryer , Rotary Dryer & Tunnel Dryer are some example of
these types.
3. Evaporation:

Open pan evaporators and multiple effect evaporators as used in

sugar and salt industries for example. Among these halogen family
we have technology to separate chlorine and fluride but production
of bromine from the 'sea brine'is almost not put into practice as the
bromine chemicals is highly corrosive and necessary precaution has
to be laid out for practical purpose.
4. Extraction:

 Liquid - Liquid Extraction

Solid - Liquid Leaching are examples for this process
5. Fluid Handling Equipments:
Centrifugal pumps
Reciprocating pumps
Jet ejectors

6. Fluid - Solid Contacting:

Fixed Bed
Fluidized Bed
Moving Bed, etc.

7. Fluid - Solid Separation:

Centrifugation
Settling Tank / Sedimentation
Wet Scrubber / Dry Scrubber
Crystallization
Rotary Filter
Filter Press
Cyclone Separator
Electro-static Preciptator
Bag Filter
Thickeners based on Kynch Theory

Gas Holders
Tanks
Pressurized Spheres
Underground Caverns which are used for the purpose of
Natural Gas Storage.

8. Fluid Storage:

9. Gas - Liquid Contact:

Absorption
Stripping

10.Heat Exchangers:

Fired Heaters
Re-boilers
Condensers
Shell & Tube Heat Exchangers
Jacketed Kettle
Quenching applied in conventional Heat Transfer and
Metallurgical Operations.

11.Membrane Separation:
Dialysis
Gaseous Diffusion

12.Mixing:

Agitation
Solids Blending

13.Size Reduction & Enlargement:

Crushing
Grinding
Pelletizing

14.Solids Handling:

Pneumatic Conveying - Juices transfered to 200 km in Brazil

Bucket Elevators - Coal Industries
Screw Conveyors - Tooth Paste, Turbine Liquids
Belt Conveyors

Screening
Elutriation
Froth Rotation
Jigging
Magnetic Separation

15.Solid - Solid Separation:

CHEMICAL REACTORS

The Reactor is the heart of the chemical process. The design of an

industrial chemical reactor must satisfy the requirements in four
main areas.
1.
2.
3.
4.

Chemical Factors
Mass Transfer Factors
Heat Transfer Factors
Safety Factors

1. Chemical Factors:

This involve the kinetics of the reaction weather it's first order or
second order and based on this chemical reaction engineering
is built on the design must provide sufficient residence time to
proceed the reaction for the required degree of reaction and
conversion to product.
2. Mass Transfer Factors:

The reaction rate of homogeneous reaction may be controlled by the

rate of diffusion of reactants rather than the chemical kinetics
of Langmuir isotherm and Frendlich isotherm.
3. Heat Transfer Factors:

These describes weather the reaction is exothermic or endothermic.

In Exothermic, heat is released outside and In Endothermic, heat is
absorbed by reactants. The value of heat of reaction is necessary to
operate the chemical reactor.
4. Safety Factors:

This involve the confinement of any hazardous reactant and

products as well as the control of reaction and process conditions.
Based on these factors the Reactor Types as follows;

a. Mode of Operation - Batch or Continuous

b. Phases Types - Homogeneous or Heterogeneous
c. Reactor Geometry - Flow Pattern & Process of contacting the
phases.
The five major classes of Reactor;
i. Batch
ii. Stirred
iii.Tubular
iv.Packed Bed (Fixed)
v. Fludised Bed

Compounds like pigments, dye stuffs, pharmaceuticals and

polymers are manufactured by Batch Processes.
The Latest Heat Exchangers are Direct or Contact Exchangers In
addition to Double Pipe Exchanger, Shell & Tube Exchanger and
Plated Frame Exchanger.
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