CHI 423 Assignment 17114010

Name: Harshit K. Choudhary

Roll No: ​17114010
Department: Materials Science and Technology

Assignment
CHI 423: End semester 2019-20

1. Each question starts with a new page. Heading of the page denotes
the question number.
2. The opening statement (in italics) of the page is an assigned
question.
3. The answers are combined in the form of text and images. Text is
used for descriptions, reasoning and related contents. Images are
used for graphical illustrations, mathematical derivations and related
content.
4. The key points/ final results of the answer are in bold

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CHI 423 Assignment 17114010

Questions
1. What do you understand by the term catalyst deactivation and
regeneration? What are the different mechanisms by which a
catalyst can get deactivated?
2. How is catalyst deactivation different from catalyst poisoning?
3. What is catalytic converter? What do you understand by the term
two-way catalysis and three-way catalysis? What catalyst are used
on monolithic substrate for the purpose?
4. What do you understand by the term ‘oxygen storage materials’ in
relation to catalytic converter?
5. (a) What are the different ways by which fuels cells are classified? (b)
Why ultrapure H​2​ is required for PEMFC? (c) What is the mechanism
of oxygen reduction at the cathode of SOFC?

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CHI 423 Assignment 17114010

Solution 1
Catalytic Deactivation​: Catalyst deactivation is the loss of catalytic activity
and/or selectivity, over time.
A catalyst is a substance that changes the rate of a chemical reaction
without itself appearing in the products and ideally remains unchanged
after the completion of the reaction. But, due to chemical, mechanical or
thermal processes, the catalyst may get less effective due to deactivation.
Heterogeneous catalysts are more prone to deactivation.

Catalyst regeneration​: Technique to reuse the utilised catalyst again in

the process.
Despite our best efforts to prevent it, the loss of catalytic activity in most
processes is inevitable. When the activity has declined to a critical level.
The technique of regeneration and reuse is almost always preferred; The
ability to reactivate a catalyst depends upon the reversibility of the
deactivation process.
The decision to regenerate/ recycle or discard the entire catalyst depends
largely on the rate of deactivation. If deactivation is very rapid, as, in the
coking of cracking catalysts, repeated or continuous regeneration
becomes an economic necessity.

Different mechanisms of catalyst deactivation:​ (Source: Research

Review 1​​ )
● Poisoning: ​It is a chemical process. In this process, strong
chemisorption of species on catalytic sites occurs which block sites
for the catalytic reaction.
● Fouling: ​It is a mechanical process. In this process, physical
deposition of species from the fluid phase occurs onto the catalytic
surface and in catalyst pores.

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CHI 423 Assignment 17114010
● Thermal degradation and sintering: ​It is a thermal process. In this
process, thermally induced loss of catalytic surface area, support
area, and active phase-support reactions occur.
● Vapour formation: ​It is a chemical process. In this process, the
chemical reaction of gas with the catalyst phase occurs, to produce a
volatile compound.
● Vapour-solid and solid-solid reactions: ​It is a chemical process. In
this process, the reaction of vapour, support, or promoter occurs with
catalytic phase to produce an inactive phase.
● Attrition/crushing: ​It is a mechanical process. In this process, loss
of catalytic material due to abrasion occurs; or loss of internal surface
area due to the mechanical-induced crushing of the catalyst particle
occurs.

Also, based on kinetics, mechanism of catalyst deactivation can be

classified as (Source NPTEL 2​​ )

● Parallel deactivation​: Reactant (A) produces a side product (P)

which can deposit on the surface thereby deactivating it. Deposition
depends on reactant concentration.
● Series deactivation​: Reaction product (R) can decompose or react
further to produce material (P) that deposits and deactivates the
surface. In this case, deposition depends on product concentration.
● Side-by-side deactivation:​ In this mechanism, impurity in feed (P)
deposits on the surface deactivating it. Deposition depends on the
concentration of impurities in the feed.
● Independent deactivation​: This catalyst decay involves structural
modification or sintering of catalyst surface caused by exposure of
catalysts to extreme conditions such as high temperature. This decay
is dependent on the time that the catalyst spends in high-temperature
conditions and is independent of the materials in the fluid.

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CHI 423 Assignment 17114010

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CHI 423 Assignment 17114010

Solution 2
Catalyst poisoning ​is one of the types of ​catalyst degradation.
Catalyst deactivation refers to the broad set of mechanisms through which
a catalyst loses its activity and/or selectivity. The deactivation might be
through poisoning, thermal decomposition, Adsorption (Physical or
Chemical), Phase transformations and Mechanical Damaging etc. Whereas
Catalyst Poisoning refers to the partial or complete deactivation of a
catalyst specifically through chemical deactivation. Although poisoning is
generally undesirable, in some cases poisoning does help in improving the
selectivity of Catalysts.
Poisoning​ is the strong chemisorption of reactants, products, or impurities
on sites otherwise available for catalysis. Thus, poisoning has operational
meaning; that is, whether a species acts as a poison depends upon its
adsorption strength relative to the other species competing for catalytic
sites. In addition to physically blocking of adsorption sites, adsorbed
poisons may induce changes in the electronic or geometric structure of the
surface. Finally, poisoning may be reversible or irreversible.
(Source Research Review 1)

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CHI 423 Assignment 17114010

Solution 3
The ​catalytic converter ​is a device which reduces the harmful emissions
created in the exhaust system of an engine. The main purpose of a
catalytic converter is to reduce the harmful exhaust gases, which the
engine creates during combustion of fuel emissions.

The catalytic converter reduces the harmful exhaust gases through

chemical reactions. It reacts with the harmful pollutants in the exhaust
gases and turns them into lesser harmful gases. The catalytic converter
consists of a special catalyst. It is made of platinum and palladium which
carries out the chemical reactions.

Catalytic converters are used in exhaust systems to provide a site for the
oxidation and reduction of toxic by-products (like nitrogen oxides, carbon
monoxide, and hydrocarbons) of fuel into less hazardous substances such
as carbon dioxide, water vapour, and nitrogen gas.
(Source: Wikipedia Catalytic Converter)

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CHI 423 Assignment 17114010
i) ​Two-way catalytic converters
A two-way catalytic converter is based on oxidation and has two
simultaneous tasks:
Oxidation of carbon monoxide to carbon dioxide:
Oxidation of hydrocarbons (unburnt and partially burnt fuel) to carbon
dioxide and water:
This is mainly used to reduce hydrocarbon and carbon monoxide
emissions.

ii) ​Three-way catalytic converters

A three-way catalytic converter is based on oxidation-reduction and has
three simultaneous tasks:
Reduction of nitrogen oxides to nitrogen and oxygen
Oxidation of carbon monoxide to carbon dioxide
Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water
This is mainly used to reduce hydrocarbon and carbon monoxide
emissions, and also works on oxides of nitrogen.

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CHI 423 Assignment 17114010

Monolithic Substrate:

Monolithic Substrate ​supports the catalyst. It​ ​is the main component of
many catalytic converters, mostly in diesel particulate filters, and some
catalytic reactors. Most catalytic converters are used for vehicle emissions
control for reducing air pollution from fossil fuel power stations.
Monoliths for automotive catalytic converters are made of a ceramic that
contains a large proportion of synthetic cordierite, 2MgO•2Al​2​O​3​•5SiO​2​,
which has a low coefficient of thermal expansion.

Many small holes provide a ​larger surface area​. High surface area
facilitates catalytic reaction or filtration. The ​open spaces ​in the
cross-sectional area ​make resistance to the flow of gases through the
holes low, which ​minimizes energy ​consumed forcing gases through the
structure.
After the monolith is complete, ​a washcoat is applied ​that deposits oxides
and catalyst(s) (most commonly platinum, palladium, and/or rhodium) on
the walls of the holes.
(Source: Research Article 4​​ )

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CHI 423 Assignment 17114010

Solution 4
A three-way catalyst (TWC) converts the primary pollutants in exhaust gas
from automobiles into carbon dioxide, water and nitrogen. The highest
conversion efficiency can be achieved by maintaining a stoichiometric
composition at the TWC. TWCs contain material which store and release
oxygen (O​2​) to aid this process.

Oxygen storage materials ​are necessary for storing excess oxygen in an

oxidizing atmosphere and releasing it in a reducing atmosphere. Through
oxygen storage and release, a buffer is obtained against fluctuations in
exhaust gas composition during vehicle operation, enabling the system to
maintain a stoichiometric atmosphere in which NOx, CO and HC can be
converted efficiently.

Ceria (CeO​2​) was the first material to be recognized as having promising

oxygen storage properties. Later on, the CeO​2​-ZrO​2​ solid solution was
found to have superior oxygen storage capacity and thermal stability as
compared to CeO2. The material’s oxygen storage capacity is being
enhanced up to the theoretical limit in real catalysts. In addition to their
capacity for oxygen storage and release, oxygen storage materials can
suppress the sintering of supported noble metals, and enhance hydrogen
formation under a reducing atmosphere.

(Source: Research article 5​​ )

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CHI 423 Assignment 17114010

Solution 5a
A fuel cell is an electrochemical cell that converts the chemical energy of a
fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity
through a pair of redox reactions.
Fuel cells can be classified based on ​the electrolyte used​, ​charge
carriers​, ​operating temperature​, ​the catalyst used​, ​cell components
and ​fuel compatibility​. There are five major types of fuel cells,
differentiated from one another by their electrolyte:
1. Polymer electrolyte membrane fuel cell (PEMFC)
2. Phosphoric acid fuel cell (PAFC)
3. Alkaline fuel cell (AFC)
4. Molten carbonate fuel cell (MCFC)
5. Solid-oxide fuel cell (SOFC)
(Source: Wikipedia - Fuel_cell 6​​ )
PEMFC PAFC AFC MCFC SOFC

Electrolytes Polymer Liquid Liquid KOH Molten Ceramic

membrane H​3​PO​4 immobilised Carbonates
immobilised

Charge H​+ H​+ OH​- CO​3​2- O​2-

Carrier
Operating 80 °C 200 °C 60 - 220 °C 650 °C 600 - 1000
Temperature °C

Catalyst Platinum Platinum Platinum Nickle Perovskite

Cell Carbon- Carbon- Carbon- Stainless Ceramic

Components based based based steel based based

Fuel H​2​ - H​2 H​2 H​2 ​, CH​4 H​2 ​, CH​4​,

Compatibility methanol CO

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CHI 423 Assignment 17114010

Solution 5b
Proton-exchange membrane fuel cells (PEMFC), are mainly used for
transport applications, as well as for stationary fuel-cell applications and
portable fuel-cell applications.
Their distinguishing features include lower temperature/pressure ranges
(50 to 100 °C) and a special proton-conducting polymer electrolyte
membrane. PEMFCs generate electricity and operate on the opposite
principle to PEM electrolysis, which consumes electricity.

The need for ultrapure H​2​:

The platinum catalyst used in PEMFC is easily poisoned by carbon
monoxide (no more than one part per million is usually acceptable) and the
membrane is sensitive to things like metal ions, which can be introduced by
corrosion of metallic bipolar plates, metallic components in the fuel cell
system or from contaminants in the fuel/oxidant. Thus ultrapure hydrogen is
required for PEMFC fuel cells.

(Source: Science Direct -proton-exchange-membrane-fuel-cells 7​​ )

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CHI 423 Assignment 17114010

Solution 5c
A ​solid oxide fuel cell (or SOFC) ​is an electrochemical conversion device
that produces electricity directly from oxidizing a fuel. Fuel cells are
characterized by their electrolyte material; the SOFC has a solid oxide or
ceramic electrolyte. (Source: Wikipedia Solid_oxide_fuel_cell 8​​ )
The cathode, or air electrode, is a thin porous layer on the electrolyte
where oxygen reduction takes place. The overall reduction reaction is
written in Kröger-Vink Notation is as follows:

Diagramatic schema of the cell is:

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CHI 423 Assignment 17114010
Bibliography

1. Argyle, M. & Bartholomew, C. Heterogeneous Catalyst

Deactivation and Regeneration: A Review. ​Catalysts​ ​5,​ 145–269

(2015).

2. NPTEL – Chemical Engineering – Catalyst Science and Technology

Chapter 25 Catalyst Deactivation

3. Wikipedia - Catalytic_converter

4. Baharudin, L. & Watson, M. J. Monolithic substrate support

catalyst design considerations for steam methane reforming

operation. ​Reviews in Chemical Engineering​ 34, 481–501 (2018).

5. A review on oxygen storage capacity of CeO2-based materials:

Influence factors, measurement techniques, and applications in

reactions related to catalytic automotive emissions control - Ping Li,

Xiaoyin Chen, Yongdan Li, Johannes Schwank; Catalysis Today -

2019

6. Wikipedia - Fuel_cell

7. Science Direct: proton-exchange-membrane-fuel-cells

8. Wikipedia - Solid_oxide_fuel_cell

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