Module 3.

Industrial Chemistry and Process Design

Major topics
in this
module

Role of Catalysts

A catalyst is a substance that

Definition increases the rate of a
chemical reaction without
being consumed in the
process.
• Catalysis is the process by
which a catalyst increases
the rate of a chemical
reaction

[Link]
affect-reaction-rates-16-18-years/[Link]
Types of A homogeneous catalyst is present in the same phase as
catalysts the reactants.
A heterogeneous catalyst is present in a different phase
from the reactants

Homogeneous The catalyst and the reactants are in the same single
catalyst phase, usually a liquid or gas.
• The reaction occurs throughout the mixture in a
uniform way
• Example: sulphuric acid for the ester hydrolysis of ethyl
acetate
tason ,
Choon+
Ch1005
Heterogeneous Heterogeneous catalysts are chemical catalysts whose
catalyst physical phase is different from the physical phase of
the reactants and/or products that take part in the
catalyzed chemical reaction.
• Most heterogeneous catalysts are solids that act on
substrates in a liquid or gaseous reaction mixture.
• Example: vanadium pentoxide for oxidation of sulfur
dioxide into sulfur trioxide by the contact process

• Haber Process : Production of ammonia from

hydrogen and nitrogen using Fe as the catalyst
 [Link]
Supplemental_Modules_and_Websites_(Inorganic_Chemistry)/Catalysis/Examples/
Examples_of_Catalysis/1._An_Introduction_to_Types_of_Catalysis

Homogeneous catalysis vs Heterogeneous catalyst

Enzymatic Enzymatic catalysis is the process by which enzymes,

catalysis which are biological molecules(mostly proteins) increase
the rate of biochemical reactions.
Enzymes are highly efficient and specific, meaning each
enzyme typically catalyzes only one or a few types of
reactions.
Example: Digestion in the human body. Amylase (an
enzyme) in the saliva breaks the chemical bonds within
the large starch molecules converting them into smaller
sugar molecules like maltose
 Heterogeneous catalysis is crucial in producing the bulk
Why is
and fine chemicals used in modern chemical process
Heterogeneo
development.
us Catalysis
Important?

Mechanism of
heterogeneou
s catalysis:
Surface
adsorption
Theory
 Iodine clock reaction: An interesting video
[Link]

Chemical kinetics

• Branch of chemistry, which deals with the study of

reaction rates and their mechanisms, called chemical
kinetics.
• The word kinetics is derived from the Greek word ‘kinesis’
meaning movement

Significance
of chemical
kinetics in
Industry

Rate of a • The speed of a reaction or the rate of a reaction can

Chemical be defined as the change in concentration of a reactant
Reaction or product in unit time.
• To be more specific, it can be expressed in termsof:
• (i) the rate of decrease in concentration of any one of
the reactants, or
• (ii) the rate of increase in concentration of any one of
the products.

[Link]
Map%3A_Chemistry_-_The_Central_Science_(Brown_et_al.)/
14%3A_Chemical_Kinetics
• Consider a hypothetical reaction with assuming that the
volume of the system remains constant
• One mole of the reactant R produces one mole of the
product P.
• If [R]1 and [P]1 are the concentrations of R and P
respectively at time t1 and
[R]2 and [P]2 are their concentrations at time t2 then,
Unit of rate of
reaction

Dependence • The representation of rate of reaction in terms of

of Rate on concentration of the reactants is known as rate law.
Concentration • It is also called as rate equation or rate expression
Rate law

Order of a • The sum of powers of the concentration of the reactants

in the rate law expression is called the order of that
Reaction
chemical reaction.
• Order of a reaction can be 0, 1, 2, 3 and even a
fraction.
• A zero order reaction means that the rate of reaction is
independent of the concentration of reactants.
Units of rate
constant

Zero order
reactions
 Catalytic converter:

[Link]

Industrially Example 1: Catalytic Oxidation of Carbon Monoxide on

significant Platinum Surface
Zero order
reactions Zero-order nature: At higher CO pressures, the catalyst
surface becomes saturated with CO molecules, making the
reaction rate independent of CO concentration.
•Industrial relevance: Catalytic converters used in
automobiles to reduce CO emissions.

First order
reactions
 Industrially Example 1: Radioactive Decay Reactions
significant • Decay of Uranium-238 Thorium-234 + α-particle
First order
• Reaction order: Always follows first-order kinetics.
reaction
• Industrial importance: Nuclear energy production,
Medical uses (radioisotopes in diagnosis and therapy).

• Increase in temperature leads to increase in the rate of

Temperature
reaction for most of the reactions.
Dependence of
• For a chemical reaction with rise in temperature by 10°
the Rate of a
, the rate constant is nearly doubled.
Reaction
• The temperature dependence of the rate of a chemical
Arrhenius reaction can be explained by Arrhenius equation
equation

[Link]
radioactivity-alpha-decay/
Significance
of
Activation
energy in
industries
 [Link]

Green Chemistry
Green chemistry is an area of chemistry and chemical
Definition engineering focused on the design of products and
processes that minimize or eliminate the use and
generation of hazardous substances

12
Principles
of green
chemistry

Principle 1: Principle 1: It is better to prevent waste than to treat

Prevention or clean up waste after it is formed.
of waste
• E-Factor, or Environmental Impact Factor, concept
introduced by Roger Sheldon in 1992.
• This metric helps to quantify the amount of waste
generated per kilogram of product.
• It is a means to assess the ‘‘environmental
acceptability’’ of a manufacturing process.
• The environmental factor which has been adopted by
many in the chemical industry.
Example 1: Synthesis of ethylene oxide
Traditional method to synthesis ethylene oxide
• Ethylene oxide prepared through a chlorohydrin
intermediate.

• For each kilogram of product, 5 Kg of waste were to be

disposed.
• Due to E- factor this method is not a green method
Alternative green method
• Ethylene reacts with molecular oxygen, forms ethylene
oxide.
• This method does not require chlorine.
• The E- Factor dropped to 0.3 Kg of waste.
Principle 2 While preparing any compound, synthetic methods should
Atom be designed to maximize incorporation of all materials
economy (atoms) used in the process into formation of the final
product.

Principle 3. In green chemistry chemical synthesis which uses

Less less hazardous chemicals is preferred
hazardous
chemical Examples 1: Industrial Synthesis of chlorine and caustic
synthesis soda
• Traditional method: Mercury cell process for the
synthesis of chlorine and
caustic soda from sodium chloride in chlor-alkali industries.
• This creates large amount of mercury as a waste. So it is
not a green method

New method (green method): Membrane

cell method: The most common chloralkali
process involves the electrolysis of aqueous
sodium chloride (a brine) in a membrane cell.
• A membrane, such as one made from Nafion.
Here no heavy metal is involved
 [Link]
chemistry-challenge-1996-greener-reaction-conditions-award
[Link]
challenge-2014-designing-greener-chemicals-award

Examples 2: Polystyrene foam

• Traditional method of synthesis of polystyrene foam
sheet: In the manufacture of polystyrene foam sheet
packing material, chlorofluorocarbons were used which
contribute to ozone layer depletion
• Green method of synthesis of polystyrene foam
sheet: CO2 as the blooming agent for the manufacture
of polystyrene foam sheet packing material

Chemical products should be designed in such a way

Principle 4.
that they are effective as well as less toxic and has
Designing
better safety
safer
Example 1. Designing safer chemicals
chemicals
• Traditional method of preparing Firefighting foams:
Firefighting foams suppress combustion by smothering
burning fuels and cooling fires.
• For years, these foams have used long- chain fluorinated
surfactants as the “active ingredient”.
• These long-chained fluorosurfactants are
persistent, bioaccumulative, and toxic.
Award winning green method (EPA-2014) for preparing
firefighting foams: Solberg Company developed a line of
halogen-free foam concentrates. RE-HEALING Foam
concentrates are a blend of hydrocarbon surfactant(s), water,
solvent, sugars, a preservative, and a corrosion
inhibitor .
Principle 5.
Safer
solvent and
auxiliaries

Principle 6.
Design for
energy
efficiency

[Link]
challenge-2014-greener-reaction-conditions-award#podcast
Principle 7: Disadvantages of petrochemicals
Use of Any alternatives to petro-
renewable based chemicals?
materials

Use of renewable materials

• Replacement of petroleum based products with

renewable materials.
• Example 1: Instead of petroleum based plastics, one can
use plant or
bacteria derived plastics.
• Examples of bioplastics are PLA, PGA etc
• Use of biomass for energy (eg. Biogas)
• Use of materials such as, cellulose, chitin, chitosan,
lignin, etc

• Derivatization is defined as the use of blocking groups,

Principle 8:
protection/deprotection, and temporary modification of
Reduce
physical/chemical processes.
derivatives
• It should be minimized or avoided because
derivatization require additional reagents and can
generate waste.
 Chemical products should be designed so that at the end
Principle 10:
of their function they break down into innocuous
Biodegradati
degradation products and do not persist in the
on
environment.
Example 1. Bio-degradable plastics
Examples; poly-3-hydroxybutyrate (PHB),
polyhydroxyvalerate (PHV), Polylactic acid

Principle 11:
Analysis
(real time
analysis for
pollution
prevention)
• According to the ‘‘Chemical accident prevention and the
clean air act amendments of 1990,’’ preventing accidents
Principle 12:
starts by identifying and assessing the hazards.
Accident
• All types of hazards whether it is toxicity, physical
prevention
hazards such as explosivity or flammability, and global
hazards should be addressed in the design of chemicals
and processes in order to prevent accidents such as
Bhopal or the Love Canal incident.
 Process flow diagram in chemical industries

• Process flow diagrams help us understand the chemical

process.
• These diagrams are fundamental and provide the overall
details of the process.
• The PFD shows the general arrangement of the process units
in a plant.
• The PFD should include all major unit operations and
supporting systems, such as utilities.
• It does not show detailed information or operating conditions.

Example