2010 July Semester

CAB 4433
Reactor Design for Petrochemicals

Yoshimitsu Uemura
Department of Chemical Engineering
 Objective

To provide students with a good understanding of:

- Fundamental of catalyst and catalyst technology
- Catalyst materials and properties
- Solid catalysed reaction
- Catalyst deactivation
- Fluid – Fluid reaction
- Fluid – Particle reaction
- Catalytic reactor design and its application for
petrochemical industries
 Course outcomes

At the end of this course, students should be able to:

- apply the concept of catalytic reactor for design
purposes.
- explain the mechanism of catalytic reaction
- interpret reaction and characterization data for
catalytic reactions
- identify critical parameters affecting the
performance of reactor
- integrate the principles of catalytic reactor in
practice through laboratory work
 Assessment

Quiz/ Test/ Assignment -50%

Laboratory -10%
Final examination -40%
 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
 Ammonia synthesis
SOCIETY ACADEMIA
At the end of the 19th Controversy on the
century, demand for the equilibrium constant of :
basic fertilizers P, K and N N2 + 3H2 = 2NH3
increased in Europe ∆H(500ºC)=-109kJ/mol-N2
because of increase in
population. 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

Fe-Al2O3-K2O
ammonia per day was built in Germany.

Today, more than 600 large scale plants worldwide, the Alkali promoted
annual production is over 160 million tons. Ru/C or Ru/MgO
Effects of temperature and pressure on NH3
equilibrium

101.3kPa, 300K
NH3 concentration [%]

Eq. NH3 = 98%

Required to raise the

temp.in order to obtain
sufficient catalytic activuty.

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

 Labo reactor for NH3 synthesis used by Haber
H2 + N2
Heater

Catalyst bed

High pressure High pressure

vessel 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

Liquefied ammonia
Compressor

H2 + N2

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2nd 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).
 Wheat yield in France

Annual NH3 production

Yield [t/ha]

2.7 million ton (worldwide)

85 million ton
The first NH3 plant

60 million ton
Annual N consumption
12 million ton 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

Japan
Yield [t/ha]

Applied N fertilizer [kg-N/ha]

H. Kawashima, World Food Production and Biomass Energy, Tokyo Daigaku Shuppan-kai (2008).
Applied amount of N fertilizer/field area
Applied N fertilizer [kg-N/ha]

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

Annual crop production

Relative magnitude

Population

Annually, 350 kg-crop per capita

Year

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

Troposphere

Organic N Organic N

Sea
Land
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 2nd 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, 350-500ºC) and vacuum residue (>C40, >550ºC) are
cracked to gasoline range hydrocarbons (C5-C10, 70-220ºC)

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

Catalysis Abstract
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
When it occurs in
of catalysis is the same.
homogeneous phase such as
A*(without cat) liquid phase, it is called
homogeneous catalysis.
Energy level

A* (with cat)

A
B
When it occurs on solid
surface, it is called
Reaction coordinate heterogeneous catalysis.

A → A* → B
Reactant Activated Product
complex
(unstable, short life)
 Homogeneous catalytic reaction
Partial oxidation of ethene to produce acetaldehyde (Wacker reaction)

Ethene partial oxidation

Catalytic
H2C=CH2 + H2O + PdCl2 → CH3CHO + Pd + 2HCl (1)
Pd2+ regeneration
Pd + 2CuCl2 → PdCl2 + 2CuCl (2)
Cu2+ regeneration
2CuCl + (1/2)O2 + 2HCl → 2CuCl2 + H2O (3)

Overall reaction
H2C=CH2 + (1/2)O2 → CH3CHO (1) + (2) + (3)
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 2nd 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 2nd ed., Wiley Interscience (2006).
 Heterogeneous catalyst
-the reason for porous structure-
 Heterogeneous catalyst
-the reason for porous structure-
 Typical pore structure of
catalyst (support)

C. H. Bertholomew et al., Fundamentals of Industrial Catalytic Processes 2nd ed., Wiley Interscience (2006).
Heterogeneous catalytic reaction
-intrinsic reaction (overall)-
→ Hydrogenation of ethene
On metal (Pt, Ni etc) surface
← Dehydrogenation of ethane

Pt
CH2=CH2 + H2 ↔ CH3CH3
 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 2nd ed., Wiley Interscience (2006).
 Comparison of homogeneous
and heterogeneous catalysts

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

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

Measures of reaction rates
Homo- Hetero-
Homogeneous Heterogeneous geneous geneous
catalytic catalytic non- non-
catalytic catalytic

No Yes? No No

Yes Yes No No

No Yes (Short time No No

use in lab)

No Yes (Analysis for No No

cat. one particle)

Yes No Yes Yes

No No No Yes