Chemical Process Industries

Hemant Kumara Balsora

Chemical engineering department
[email protected]
 Course Outcomes
CH2206 : Chemical Process Industries
1. Develop fundamental understanding of the process carried out in chemical
industry
2. Explain the basic reaction steps involved in the production of various grades
of products.
3. Construct process flow diagrams for different chemical manufacturing plants.
4. Predict all possible trouble shootings arise in chemical plants.
5. To review the practical importance and relevance of process takes place in
chemical industry
6. Resolve all technological and economical problems arise in the chemical
manufacturing plants.
 INTRODUCTION
In general , all the Chemical production processes involves mainly three major
steps:
1.Mixing
2. Process/reactions
3. Separation
Production of Washing soda (Na2CO3 ) 2 NaCl + CaCO3 → Na2CO3 + CaCl2

NaCl, separator CaCl2

Mixer Reactor
CaCO3,
Na2CO3 

“Every industrial chemical plant is based on Unit Operations (physical treatment) and Unit Process (chemical
treatment) to produce economically a desired product from specific raw materials.”

3
 UNIT PROCESS & UNIT OPERATION

“Unit process: It involves the changes in composition, character and properties of materials and
are most often affected or controlled by temperature and pressure changes.”
Examples: Nitration, Halogenations, Hydrolysis, Hydration, Oxidation, Sulfonation
etc
“Unit operation: It involve the addition or removal of some form of energy in contacting,
transport and conditioning of materials by physical means , without chemical changes.”

Examples: Heat transfer operations , mass transfer operations, size reduction, filtration,
separation, etc.

4
5
 Unit Processes
 Nitration is a chemical reaction by which nitro (NO2) groups are introduced into
molecule (organic compounds.) most frequently by electrophilic action of the
nitronium ion (NO2+).
 Sulphonation is the introduction of one or more sulfonic acid group (-SO3H) into
an organic compound or into intermediates.
 Halogenation is a chemical reaction that involves the reaction of a compound with
a halogen and results in the halogen being added to the compound. Organic
compounds undergo halogenations much more often than inorganic compounds.
 Oxidation is the loss of electrons during a reaction by a molecule, atom or ion.
Oxidation occurs when the oxidation state of a molecule, atom or ion is increased.
 Hydrogenation involves the reaction of a substance with hydrogen in the presence
of catalyst.
 Alkylation involves the introduction of an alkyl radical into an organic compound
by substitution of reduction
6
 UNIT OPERATIONS

Fluid flow operation: Branch of science which deals with behavior of fluids (liquids and Gases) at rest as well as
motions.

Heat transfer: It deals with study of rates at which exchange of heat takes place between a source and a receiver.
“Transformation of energy from one body to another body or one part to another part of the same body due to
temperature driving force.”

Mass transfer: Mass transfer deals with transport of a species in a mixture in a single phase or phase across a
phase boundary in the presence of concentration driving force.

Evaporation: Evaporation is an operation that carried out in an industries as a means of concentrating a weak
liquor/solution by vaporization of portion of solvent. The objective is to concentrate a solution consisting of non -
volatile solute and volatile solvent.

Drying: Removal of moisture from the solid. (“ mass transfer from solid to gas phase”.)

7
 UNIT OPERATIONS
Gas Absorption: Removal gas component from the gas mixture by passing through solvent
(liquid). “ mass transfer from gas phase to liquid phase.”

Adsorption: Components of gas or liquid mixture can be adsorbed on the surface of a solid
adsorbents.

Leaching: leaching is the separation of a component of the solid by selectively dissolving the
soluble components in the suitable solvent.

Distillation: The separation of liquid mixtures into their various components by using thermal
energy. Or separation of components based on the boiling point difference.

Mixing: Mixing is the reduction of inhomogeinity in order to achieve a desired process result.

Other unit operation: Filtration, size reduction, sedimentation..etc.

8
Batch & Continuous operation/process.
The manufacturing industry has drawn its efficiency from large-scale continuous processes
over a long period. Initially, the manufacturing facility for a new product used to be either
a batch process or a laboratory process on a larger scale.

But as the economy of scale was key to success in business, chemical engineering and
process industries focused all attention on designing and developing continuous processes.

Continuous processes are dominant in manufacturing of bulk chemicals.

However, for manufacturing fine and specialty chemicals, with the increased emphasis on
and customer requirements of high quality, equal focus has been on batch processing.

9
 FA0
UO/UP

UO/UP FA1
Batch process
Continuous process
A batch process is a process that leads to the
In a continuous process, there is
production of finite quantities of material by
continuous flow of material or product.
subjecting quantities of input raw materials
Processing the materials in different
to an ordered set of processing activities over
equipments produces the products. Each
a finite period of time using one or more
equipment operates in a single steady
equipment's.
state and performs specific processing
Some examples of batch processes are beverage function. Some examples of continuous
processing, biotech products manufacturing, processes are generation of electricity,
dairy processing, food processing,pharmaceutical Cement production, paper mill and so on
formulations and soap manufacturing
10
 Batch Process: Advantages/Disadvantages
Advantages
 Batch processing allows production of multiple different products or different product grades in the
same equipment.
 In a batch plant , the integrity of a batch is preserved as it moves from operation to operation. This can
be very useful for quality control purposes
 The production rate of batch plants is very flexible, as there are no turndown issues when operating at
low output.
 Batch plants are easier to clean and maintain in sterile operation.
 Batch processes are easier to scale up
 Batch plants have low capital for small production volumes. The same piece of equipment can often be
used for several unit operations.

11
 Batch Process: Advantages/Disadvantages

Disadvantages
 The scale of production is limited. It is difficult to achieve economies of scale by going to high
production rates.
 Batch to batch quality can vary, leading to high production of waste products.
 Recycle and heat recovery are harder , making batch plants less energy efficient and more likely to
produce waste by products.
 Asset utilization is lower for batch plants as the plant almost inevitably is idle part of the time.
 Batch plants are more labour intensive and so the fixed costs of production are much higher for batch
plants
 Flow charts

A flowchart is a type of diagram that represents an algorithm, workflow or

process, showing the steps as boxes of various kinds, and their order by
connecting them with arrows.

This diagrammatic representation illustrates a solution model to a

given problem. Flowcharts are used in analysing, designing, documenting or
managing a process or program in various fields

13
Block Flow Diagram (BFD)

Reaction: C7H8 + H2 = C6H6 + CH4

14
 International conventions and recommended formats for the
realization of BFDs
 The unit operations are indicated by blocks
 The main streams are identified by lines with arrows indicating the flow direction
 When possible, the direction of the streams is from left to right
 Light currents (gas) upwards, heavy currents (liquids and solids) downwards of the blocks
representing the single portions of the plant
 Provide basic and most important information of the process
 If the process lines intersect, the horizontal ones are held whilst the vertical one are broken
 Provide simplified material balances and main reactions

15
 PROCESS FLOW DIAGRAM (PFD)
The PFD is greatly enhanced compared to the BFD. It is the most important and used
diagram to describe with an adequate level of detail the structure of the process.
There is not a universally accepted nomenclature.
In general, a PFD contains the following information:
 The important equipment is shown together with a short description. Each device is
identified by a code.
 The utilities of the equipment are shown and described.
 The streams are shown and identified with a number. Every stream shows the process
conditions and composition.
 The main control loops are shown in PFD.
16
 Types of Reactor systems
1.Batch reactor
2.Continuous stirred tank reactor ( CSTR )
3.Plug flow (tubular) reactor (PFR)
 Chapter-01
Mechanisms and recent advances of following
unit processes
Alkylation and Acylation, e.g. alkylation of benzene, phenols, etc. Halogenation,
e.g. chlorination of toluene, Nitration and Sulfonation, e.g. nitration, sulfonation
of benzene, etc. Hydrogenation and Reductive Alkylations, e.g. hydrogenation of
nitrobenzene, reductive alkylation reactions of anilines, Oxidation, e.g. oxidation
of xylenes, etc.
 Nitration
Nitration is a chemical reaction by which nitro (NO2) groups are introduced into
molecule (organic compounds.) most frequently by electrophilic action of the
nitronium ion (NO2+).
Nitration of aromatic compounds is one of the most widely studied organic
reactions.
Since the nitrated products are important intermediates for pharmaceuticals,
perfumes, plastics and dyes; nitration of aromatic compounds is an
industrially consequential reaction
Nitration also plays an important role in the preparation of explosives..
For example, the most commonly used military and commercial preparation of
explosive compounds such as TNT, RDX, nitroglycerine, PETN, etc., are all
produced by nitration.
PETN-Pentaerythritol tetranitrate
 Nitration ---- continue…..
Nitration is a chemical reaction by which nitro (NO 2) groups are introduced into molecule

(organic compounds.) most frequently by electrophilic action of the nitronium ion (NO2+).
This type of nitration chemistry has been practised on an industrial scale for over 100 years.
In the manufacture of a variety of materials.
The formation of the nitronium ion occurs by disproportionation of nitric acid, which is
promoted by the presence of a second (strong acid).
Most commonly , this second acid is either sulphuric acid or oleum.
 It is basically a substitution or double exchange reaction in which one or more NO 2 groups
of the nitrating agent replace one or more groups (usually hydrogen atoms) of the compound
being nitrated.
 Role of sulfphric acid

• It reduces the ionization HNO3 H+ + NO3- ,

• It promotes the ionization of nitric acid to give NO2+

HNO3 +2H2SO4   NO2+ +H3O+ + 2HSO4-

Ionization or ionisation, is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with
other chemical changes. The resulting electrically charged atom or molecule is called an ion.
 Types of nitration
The nitration reaction can be classified into three categories as shown in Figure
C- nitration O- nitration N- nitration
(nitro compound) (nitrate ester) (nitramine)
 Application of Nitration
Nitration is used to add nitrogen to a benzene ring, which can be used further in
substitution reactions.
The nitro group acts as a ring deactivator.
Having nitrogen present in a ring is very useful because it can be used as a directing
group as well as a masked amino group.
The products of aromatic nitrations are very important intermediates in industrial
chemistry. 

Ref: http://chemwiki.ucdavis.edu/Organic_Chemistry/Hydrocarbons/Aromatics/Reactions_of_Aromatics/
Nitration_and_Sulfonation_of_Benzene
Manufacturing of Nitro benzene & Aniline
 Reaction and Raw materials
•Aniline is mainly produced in two steps from benzene.

•First, benzene is nitrated using a concentrated mixture of nitric

acid and sulphuric acid at 50 to 60 °C, which gives nitrobenzene.

•In the second step, the nitrobenzene is hydrogenated, typically at 200–300 °C

in presence of various metal catalysts.
Aniline production process: hydrogenation of nitrobenzene
Nitrobenzene Applications
Nitrobenzene is used widely in the production of aniline, which is a precursor to
rubber chemicals, pesticides, dyes (particularly azo dyes), explosives,
and pharmaceuticals.
Nitrobenzene is also used in shoe and floor polishes, paint solvents.

Aniline Applications
 The principal use of aniline in the dye industry is as a precursor to indigo.
 Aniline is used to make a wide variety of products , such as polyurethane foam,
agricultural chemicals , synthetic dyes , antioxidants, stabilizers for rubber industry,
herbicides, varnishes and explosives.
Aniline by Ammonolysis of Phenol
Reaction with ammonia in which a bond is broken and an NH2 group is
attached.

Ammonia is comparatively low cost reagent

Other routes to amines through reduction use expensive reagents (Fe,
Zn or H2 gas).
Substituted amines can be produced by using substituted ammonia
(amines) in place of simple ammonia.
Agitated pressure vessel made entirely of Iron is used.
Sulphonation
 Sulphonation
Sulphonation is the introduction of one or more sulfonic acid group (-SO3H)
into an organic compound or into dye intermediates

It is often conducted to confer water solubility , to provide fiber affinity, and
to direct other incoming groups in the steps that follow sulfonation.

The usual sulfonating agent is concentrated sulfuric acid, but sulfur trioxide,
oleum , an SO3/H2SO4 mixture, chlorosulfuric acid, metallic sulfates and
sulfamic acid are also occasionally used.
 Sulphonation

 During the sulphonation of substance, a critical concentration of acid is required below

which sulfonation ceases.

 The removal of water formed in the reaction is therefore essential.

 The use of a very large excess of acid, while expensive, can maintain an essentially
constant concentration as the reaction progresses.

 It is not easy to volatilize water from concentrated solutions of sulfuric acid, but
azeotropic distillation can be useful.
 Sulphonation
.

 The sulfonation reaction is exothermic, but not corrosive, so sulfonation can

be conducted in steel, stainless steel, or cast iron sulfonators.

 A jacket with hot oil or steam can serve to heat the reactants sufficiently to
get the reaction started, then carry away the heat of reaction.

 A good agitator, a condenser, and a fume control system are usually also
provided
 Sulfonation of Benzene
Sulfonation is a reversible reaction that produces benzenesulfonic acid by adding
sulfur trioxide and fuming sulfuric acid to benzene.

The reaction is reversed by adding hot aqueous acid to benzenesulfonic acid to

produce benzene.
Applications of Sulfonation
Because sulfonation is a reversible reaction, it can also be used in further
substitution reactions in the form of a directing blocking group because it can
be easily removed.
The sulfonic group blocks the carbon from being attacked by other substituents
and after the reaction is completed it can be removed by reverse sulfonation.
Benzenesulfonic acids are also used in the synthesis of detergents, dyes, and
sulfa drugs. 
Bezenesulfonyl Chloride is a precursor to sulfonamides, which are used in
chemotherapy.
Halogenation
 Halogenation
Halogenation is a chemical reaction that involves the reaction of a compound with
a halogen and as results, the halogen being added to the compound.
Organic compounds undergo halogenation much more often than inorganic compounds
In halogenation, due to cost difference between chlorine and the other halogens.
chlorination is mostly used, In some of the cases Br, I, or F are also used
Chlorine and hydrochloric acid are used to cause substitution (or addition) on aryl ring
compounds.
Chlorination proceeds
◦ By addition to an unsaturated bond
◦ By substitution for hydrogen
◦ Or replacement of another group such as –OH or -SO3H
Example, Chlorobenzene

It is manufactured by passing dry chlorine through benzene using

ferric chloride as a catalyst.
The chlorination of benzene produces mono-chloro-benzene (MCB) or other derivatives,
depending on the conditions of chlorination.
For example , MCB is produced in the presence of an iron catalyst at 40-60 0C and molar ratio
of benzene and chlorine of 1: 0.6.
with a lower molar ratio and in the presence of AlCl3 catalyst, o- Dichlorobenzene (DCB) is
mainly obtained.
Chlorobenzene is formed with the removal of the heat of exothermic reaction at the expense
of evaporation of the excess benzene.
Chlorination is carried out in a steel cylinder lines with acid resistant brick and packed with
iron and ceramic rings.
The temperature of reaction is maintained between 75-85 0C and it causes the excess of
benzene to evaporate.
The pure chlorobenzene is produces by the consecutive washing the crude chlorobenzene
with water and soda solution and by subsequent fractionation.
 Properties and applications
The chlorobenzene is used as a solvent ,and to manufacture phenol, dye and insecticides
It is clourless liquid with an almond-like odor and is used in making certain other chemicals,
rubber, dyes and grease solvents. It is used as a feedstock to produce ortho and para –
nitrochlorobenzenes and aniline , as solvent for paints; and as a heat transfer medium.

Chlorobenzene is moderately soluble in water up to 1000 milligrams per liter of water. It is a

flammable liquid and a fire hazard. It is unreacted towards water and decomposes only at high
temperatures.
ALKYLATION OF AMINES
 Alkylation
Alkylation is the transfer of an alkyl group from one molecule to another. The alkylation
reaction combines light C3- C5 olefins with iso-butane in the presence of a strong acid
catalyst.
Although alkylation can take place at high temperature without catalyst, the only processes
of commercial importance involve low to moderate temperatures using either sulfuric or
hydrofluoric acid.
It is usually used to increase the resistance of dyes to shade changes when exposed to dilute
alkalis or acids.
The usual alkylating agents for amines are alcohols, alkyl halides, dialkyl sulfates etc.
Jacketed autoclaves with stirrers and internal cooling coils are used.
E.g. ethylbenzene can be prepared by passing ethylene through a layer of benzene at 90-100
°C and increased pressure in the presence of anhydrous AlCl3 as catalyst and small amounts
of hydrogen chloride as catalyst activator.
OXIDATION
Oxidation is the loss of electrons during a reaction by
a molecule, atom or ion. Oxidation occurs when the oxidation state of a
molecule, atom or ion is increased.
Control is the major problem during oxidation.
Only partial oxidation is wanted as one organic compound is converted
into another.
It is simple enough to make CO2 and H2O from organic substances, but
once started, it is difficult to stop oxidation before it is completed.
The commonest reagent is air, but oxygen frequently proves to be less
expensive.
The chemical oxidizing agents includes
◦ Nitric acid
◦ Dichromates
◦ Permanganates
◦ Chromic anhydride
◦ Chlorates
◦ Hydrogen peroxide
These are generally more expensive than the gases, so they are only used when the
gases do not function well
Partial oxidation is accompanied with combustion reaction which are highly
exothermic.
Therefore heat removal is frequently the controlling factor in oxidations
Thank you