2015 September Semester

CCB 4433
Reactor Design for Petrochemicals
Lecturer:
Associate Prof Dr Suzana Yusup
Department of Chemical Engineering

Course Contents & Delivery

Introduction and fundamental of catalyst
5 hrs
Importance of catalyst and catalyst technology
Introduction to homogeneous and heterogeneous catalysis and system
Fundamental of catalytic technology
5 hrs
Adsorption isotherms
Catalysis
Application of catalyst for petrochemical processes
Catalyst materials
4 hrs
Structure
Preparation and forming of catalyst
Catalyst characterization
4 hrs
Entire catalyst
Metal on support
Heterogeneous catalytic reaction
6 hrs
Reaction kinetics
Pore diffusion resistance
Performance equation for reactors with heterogeneous catalyst
Fluid-particle reaction
6 hrs
Introduction of models
Shrinking-core model
Shrinking-particle model
Progressive conversion model
Catalytic reactor system
6 hrs
Gas-solid catalyst reactor
Fluidized bed

References
1. Fogler H. S., Elements of Chemical Reaction
Engineering, 3rd Ed., Prentice Hall, 1999.
2. Levenspiel O., Chemical Reaction Engineering,
3rd Ed., John Wiley, 1999.
3. Froment G. F. and Bischoff K. B., Chemical
Reactor Analysis and Design, 2nd Ed., John
Wiley, 1990.
4. C. H. Bertholomew et al., Fundamentals of
Industrial Catalytic Processes 2nd ed., Wiley
Interscience (2006).

Chemical Engineering Programme Outcomes (12POs)

Apply knowledge of mathematics, science and engineering fundamentals and an engineering specialisation to the
solution of complex chemical engineering problems.
Identify, formulate, research literature and analyse complex chemical engineering problems reaching substantiated
conclusions using first principles of mathematics, natural sciences and engineering sciences

Design solutions for complex chemical engineering problems and

design systems, components or processes that meet specified needs
with appropriate consideration for public health and safety, cultural,
societal, and environmental considerations. (PO3)
Investigate complex chemical engineering problems using research
based knowledge and research methods including design of
experiments, analysis and interpretation of data and synthesis of
information to provide valid conclusions. (PO4)
Use modern engineering and IT tools to evaluate complex chemical engineering activities.
Apply reasoning informed by contextual knowledge to assess societal, health, safety, legal and cultural issues and the
consequent responsibilities relevant to professional engineering practice.
Understand the impact of professional engineering solutions in societal and environmental contexts and demonstrate
knowledge of and need for sustainable development.
Apply ethical principles and commit to professional ethics and responsibilities and norms of chemical engineering
practice
Communicate effectively on complex chemical engineering activities with the engineering community and society.
Function effectively as an individual, and as a member or leader in diverse teams and in multi-disciplinary settings.
Recognise the need for, and have the preparation and ability to engage in independent and life-long learning in the
broadest context of technological change.
Demonstrate knowledge and understanding of engineering and management principles and apply these to ones own
work, as a member and leader in a team, to manage projects and in multidisciplinary environments.

Course Learning Outcomes (5CLOs)

At the end of this course, students should be able to:
CLO1. Understand and appreciate catalysis and catalyst for designing solutions for complex chemical
engineering problems
CLO2. Understand and appreciate heterogeneous catalytic and non-catalytic reactions for designing
solutions for complex chemical engineering problems
CLO3. Design flexibly solid catalysts for investigating complex chemical engineering problems
CLO4. Understand and appreciate representative catalytic and non-catalytic reactors for investigating
complex chemical engineering problems
CLO5. Design flexibly heterogeneous catalytic and non-catalytic reactors for investigating complex
chemical engineering problems

Appreciate

PO3

CLO1. Catalysis, catalyst

Design flexibly

PO4

CLO3. Solid catalysts

CLO2. Heterogeneous catalytic

and non-catalytic reactions

CLO4. Representative catalytic

and non-catalytic reactors

CLO5. Heterogeneous catalytic

and non-catalytic reactors

Assessment & Time Table

Test -40%
Assignment -10%
Final examination -50%
Week
1
2
3
4
5
6
7
8
9
10
11
12
13
14

Time & Venue

Chapter 1
Introduction and fundamental of catalyst
1. Importance of catalyst and catalyst
technology
1) Ammonia synthesis
2) Petroleum refining
2. Introduction to homogeneous and
heterogeneous catalysis

Nitrogen circulation by living creatures

N2
Fixation by microbes
200 million ton/year

NO3-

NO2-

NH4+

Amino acids

Proteins

Ammonia synthesis
SOCIETY
At the end of the 19th
century, demand for the
basic fertilizers P, K and N
increased in Europe
because of increase in
population.

ACADEMIA
Controversy on the
equilibrium constant of :
N2 + 3H2 = 2NH3
H(500C)=-109kJ/mol-N2
ACADEMIA
In 1904, NH3 was
synthesized from N2 and H2
by Haber et al.

In 1908, Haber realized it is important to develop catalytic

reactor for the synthesis.
In 1913, the first commercial plant capable of 10 tons of
ammonia per day was built in Germany.
Today, more than 600 large scale plants worldwide, the
annual production is over 160 million tons (-> 80% fertilizer).

Fe-Al2O3-K2O
Alkali promoted
Ru/C or Ru/MgO

Effects of temperature and pressure on NH3

equilibrium

NH3 concentration [%]

101.3kPa, 300K
Eq. NH3 = 98%
Required to raise the
temp. in order to obtain
sufficient catalytic activity.

P [kg/cm-2]
Catalysis Society of Japan, Basic Industrial Catalytic Reactions, Kohdan-sha (1985).

Labo reactor for NH3 synthesis used by Haber

Heater

H2 + N2

Catalyst bed

High pressure
vessel

High pressure
circulating pimp
Condenser

Liquefied ammonia

Catalysis Society of Japan, Basic Industrial Catalytic Reactions, Kohdan-sha (1985).

Commercial plant for ammonia synthesis

Catalyst bed

Ammonia
condensation

Compressor

Liquefied ammonia

H2 + N2
C. H. Bartholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Nitrogen fertilizer consumption

Consumption [Million ton-N/year]

Russia + East Europe

Europe

Asia

Other

Year
H. Kawashima, World Food Production and Biomass Energy, Tokyo Daigaku Shuppan-kai (2008).

Yield [t/ha]

Wheat yield in France

Annual NH3 production

2.7 million ton (worldwide)
85 million ton
The first NH3 plant
60 million ton
12 million ton

Annual N consumption
as N fertilizer (worldwide)

Year
H. Kawashima, World Food Production and Biomass Energy, Tokyo Daigaku Shuppan-kai (2008).

The effect of N fertilizer on yield

Crops

Vegetables

Yield [t/ha]

Japan

Applied N fertilizer [kg-N/ha]

H. Kawashima, World Food Production and Biomass Energy, Tokyo Daigaku Shuppan-kai (2008).

Applied N fertilizer [kg-N/ha]

Applied amount of N fertilizer/field area

West Europe
East Asia

South Asia

West Africa

Year
H. Kawashima, World Food Production and Biomass Energy, Tokyo Daigaku Shuppan-kai (2008).

Crop production increase sustains population increase

Relative magnitude

Annual crop production

Population

Annually, 350 kg-crop per capita

40% as crop
60% as meat via feed grains for domesticated animals

Year
H. Kawashima, World Food Production and Biomass Energy, Tokyo Daigaku Shuppan-kai (2008).

Global nitrogen circulation

Stratosphere
Troposphere

Organic N

Land

Organic N

Sea
Sediment

E. Sakurai et al., Introductory Plant Physiology, Baifuh-kan, Tokyo (1989).

Introduction and fundamental of catalyst

1. Importance of catalyst and catalyst
technology
1) Ammonia synthesis
2) Petroleum refining
2. Introduction to homogeneous and
heterogeneous catalysis

Crude oil distillation and refining

Crude
oil

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Crude oil distillation and refining

Important catalytic reactions for refining
(upgrading distilled crude oil)
1) Removing nitrogen, sulfur, oxygen and metal compounds
S and metal; to prevent catalyst deactivation at downstream processes
S and N; to reduce fuel NOx and fuel SOx
2) Cracking of heavy fractions
To obtain more light fractions (smaller carbon numbers)
Heavy gas oil (C20-C40, 350-500C) and vacuum residue (>C40, >550C) are
cracked to gasoline range hydrocarbons (C5-C10, 70-220C)
3) Reforming of naphtha
To improve gasoline quality (octane number)
Naphtha (alkanes and cycloalkanes of C5-C10) is converted to branched alkanes and
aromatics.

Reason for cracking & reforming

1. Difference between composition of crude oil and demand
2. Increase in demands of light and high octane components

BP Statistical Review of World Energy 2008

Introduction and fundamental of catalyst

1. Importance of catalyst and catalyst
technology
1) Ammonia synthesis
2) Petroleum refining
2. Introduction to homogeneous and
heterogeneous catalysis

Homogeneous and heterogeneous

catalysis
Concrete
Catalyst
A catalyst is a substrate that affects the rate of a reaction.

Abstract
Catalysis
The acceleration of a reaction by a catalyst.

Usage example
Amides are hydrolyzed to ammonium salts with catalysis
by acids or a alkalis. The acids or alkalis act as a catalyst.

Homogeneous and heterogeneous

catalysis
Basically, the principle
of catalysis is the same.

Energy level

A*(without cat)
A*

When it occurs in
homogeneous phase such as
liquid phase, it is called
homogeneous catalysis.

(with cat)

A
B
Reaction coordinate
A

Reactant

A*

Activated
complex

B
Product

(unstable, short life)

When it occurs on solid

surface, it is called
heterogeneous catalysis.

Homogeneous catalytic reaction

Partial oxidation of ethene to produce acetaldehyde (Wacker reaction)
Ethene partial oxidation
H2C=CH2 + H2O + PdCl2

CH3CHO + Pd + 2HCl

(1)

Pd + 2CuCl2

PdCl2 + 2CuCl

(2)

Cu2+ regeneration
2CuCl + (1/2)O2 + 2HCl

2CuCl2 + H2O

(3)

Pd2+ regeneration

Overall reaction
H2C=CH2 + (1/2)O2

CH3CHO

(1) + (2) + (3)

Catalytic

Homogeneous catalytic reaction

The details of the step (1) of Wacker reaction:

Activated complex

B. C. Gates et al., Chemistry of Catalytic Processes, McGraw Hill (1999).

Industrially relevant homogeneous

catalytic reaction and catalyst

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Enzymatic reaction

TCA cycle

An example of enzyme
- Rubisco in tobacco
- MW 550,000
- The enzyme for producing
biomass from CO2
A. L. Lehninger et al., Principle of Biochemistry 2nd ed., Worth Publishers (1993).

Heterogeneous catalytic reaction

-overall-

Why does a catalyst

have this kind of
porous structure?

H. S. Fogler, Elements of Chemical Reaction Engineering 4th ed., Pearson Education (2006).

A typical structure of heterogeneous

catalyst

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Heterogeneous catalyst
-the reason for fine partciles

Heterogeneous catalyst
-the reason for porous structure-

Typical pore structure of

catalyst (support)

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Heterogeneous catalytic reaction

-intrinsic reaction (overall) Hydrogenation of ethene
Dehydrogenation of ethane

CH2=CH2 + H2

Pt
CH3CH3

On metal (Pt, Ni etc) surface

Heterogeneous catalytic reaction

-intrinsic reaction (mechanism)Reaction mechanism
(Langmuir-Hinshelwood type, abbreviated as L-H type)

*: Active site of the catalyst such as Pt or Ni

B. C. Gates et al., Chemistry of Catalytic Processes, McGraw Hill (1999).

Idea of controlling step

Two extremes. How about the intermediate condition?

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Comparison of homogeneous
and heterogeneous catalysts

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2 nd ed., Wiley Interscience (2006).

Measures of reaction rates

O. Levenspiel, Chemical Reaction Engineering Third edition, John Wile&Sons (1999).

Measures of reaction rates

Homogeneous
catalytic

Heterogeneous
catalytic

Homogeneous
noncatalytic

Heterogeneous
noncatalytic

No

Yes?

No

No

Yes

Yes

No

No

No

Yes (Short time

No

No

No

No

use in lab)

No

Yes (Analysis for

one particle)

cat.

Yes

No

Yes

Yes

No

No

No

Yes