Heterogeneous Catalysis

-Intro-

CH3101- Course objectives CH3101- Course objectives

After completion of the course you should be able to:
HOW?
w Basic theory Characterization Techniques
w Provide an overview of the different characterization
and preparation techniques applied in heterogeneous Preparation Methods
catalysis. Testing Methodology
w Describe the basic theory behind each
characterization technique. w Elementary notion/understanding
Insight Structure-Activity relationship
w Choose the most adequate characterization
Reaction Mechanism
techniques and testing methods for a given
catalyst/reaction couple. w Application skills for design
Choosing the right Cat for a given reaction
w Interpret characterization and kinetic data.
w Information acquisition/processing
w Relate catalyst structure with catalytic activity for a
literature/data
certain chemical reaction. Details in course book

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 CH3101- Tools/materials CH3101- Teaching

w Course book
Moulijn/Kapteijn/Mul w Lectures - outline topics essentials
Heterogeneous Catalysis for Chemical
Engineers

w Handout materials (through Blackboard)

Transparencies lectures (essentials / extended) CH3101 Grading
Previous exams Exam(ple)s

enroll course w Written examination (80%)

HetCatCourse w Case study (20%)

further info: http://blackboard.tudelft.nl

Case Studies Case Studies

HOW? Proposed case studies

w Groups of X students
w Case studies given at the beginning of the course Methanol to olefins
(week 2)
Hydro-isomerization
w Main objective: for a given chemical conversion the
group proposes an heterogeneous catalyst along with Synthesis of Ethylene oxide via oxidation of ethylene
the most appropriate characterization techniques that Synthesis of Propylene oxide from propylene
can be applied to fully understand catalytic behavior
Methane halogenation
and the way of testing catalytic performance
w Students present their work during the last lecture Methane aromatization
day at DOW Terneuzen (no written report needed) Selective catalytic reduction (SCR) of NOx

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 CH3101- Heterogeneous Catalysis CH3101 Schedule 2017

Lecturers

Jorge Gascon
Freek Kapteijn

CH3101 March 29 Attention ! 1 ECTS ~ 28 h

3 ECTS in 9 weeks
w 7:00 Bus departs from ChemE
w 10:00 Welcome by DOW senior leader 9 hours per week
w 10:10 Introduction to Dow and opportunities for
engineers (HR) 1 day full-time per week
w 10:30 Seminar from Dow Heterogeneous Catalysis:
Research and application in Chemical Industry
w 11:30 Student presentations (poster session + lunch) attending lectures
Spending too little time can
w 15:30 Site tour and social event seriously reduce your chances reading literature
w 17:00 Departure of passing the course! studying
exam preparation

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 Attention !

Registration for the exam is -History and importance of Catalysis-

mandatory!
No registration = No exam

Catalysis Catalysis
What is a Catalyst?

- A catalyst is a substance that increases the rate of a

reaction towards equilibrium without being appreciably
consumed

How does a Catalyst work?

- A catalyst works by providing an alternative reaction
pathway to the reaction product. The rate of the reaction is
increased as this alternative route has a lower activation
energy than the reaction route not mediated by the catalyst

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 Catalysis Catalysis - Functionality

Acid Transfer

Redox Basic

Heterogeneous Catalysis -
Catalysts
Functionality
Al2O3 (g,h,q,a)
Heterogeneous surface area SiO2
Acid Transfer (non)-porous solid dispersion active phase TiO2
(un)supported strength Activated carbon
access
Dispersion Mixed oxides
ZrO2
Homogeneous
Hydrophilicity Hydrophobicity metal-organic complexes
Organo catalysts
Redox Basic
Shape Biocatalysts
selectivity enzyme
cells

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 Catalysis:
Three Levels in Catalysis
Economic Importance

Catalysts are used globally in the manufacture of over

10000 products worth over $10 trillion per year
porous carrier

More than 85 % of all todays chemical products are

(catalyst support)

bed of
produced using catalytic processes
catalyst
particles
reactants substrate product

reactor reaction desorption

Globally there are about 100 catalyst manufacturing
products
adsorption
companies
catalyst support

active site

_______________________
Source: Chem. Eng. News, GECATS roadmap

Heterogeneous Catalysis:
Global Catalyst Market
Economic Importance
Four sectors of the worlds economy critically depend on
catalysis: Sector 1995 2001
petroleum
103M$ % 103M$ %
energy production / environmental apps
chemicals production Refining 1.9 22 2.4 22
food industry
Chemical 2.2 26 2.5 19
Together these sectors account for more than 10 trillion dollars
(15%) of the worlds GDP, estimates are that catalysis Polymerisation 1.4 12 1.8 17
contributes to greater than 35% of global GDP Environmental 3.1 36 4.0 37
Total market size industrial catalysis is estimated at $ 15.2 Total 8.6 100 10.7 100
billion (2012).

_______________________ Environmental sector largest

Source: Chem. Eng. News, GECATS roadmap

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Catalyst cost per Ton of Product Price Indication of Refining Catalyst

Type of catalyst Price1990 World Market

$/kg kt/a
Reforminga 10 - 15 5
Cracking 2 350
Hydrotreating 6 50
a Price of metal not included

Historical overview New trends in Catalysis

Energy transition??

Source: Centraal Bureau voor de Statistiek (CBS)

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 Refinery capacity per region Away
Scarcity of raw materials: oil from historical distribution

Source: BP Statistical Review of World Energy 2013 Source: BP Statistical Review of World Energy 2013

Largest refineries in the world No Scarcity of Raw Materials Catalyst

longer in the West raw materials

Source: Oil and Gas Journal Source: Albemarle

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 Catalyst R&D Example:
Position of NL
Fischer-Tropsch Synthesis
http://www.fischer-tropsch.org/index.html

Fischer-Tropsch synthesis

n CO + m H2 CnH2(m-n) + n H2O

Process invented by Franz Fischer and Hans

Tropsch (1920)
More than 1000 Catalysts were tested
Widely used in Germany and Japan during 2nd World
War and in South-Africa during the Apartheid
Currently 10 plants operate worldwide

First F-T patent, 1920

Catalyst R&D Example: Catalyst R&D Example:

Fischer-Tropsch Synthesis Methanol to Olefins synthesis (MTO)

C 2 , C 3 , C 4, C 5 , C 6

Methanol

ZSM-5

Process invented by Mobil in 1974

First plant will be operative in 2011

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 Catalyst R&D Example: Catalyst R&D Example:
Methanol to Olefins synthesis (MTO) Methanol to Olefins synthesis (MTO)

Jiutai Energy Co. Ltd. Plant built in Linyi City, Shandong Province, China using
Honeywells UOP/Hydro MTO technology: in operation since 2012

Catalyst R&D Example:

Methane to Ethylene

-History and importance of Catalysis-

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