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CatalyticReaction Engineering
Professor of Industrial ChemistryDepartment of Chemical and Metallurgical EngineeringSchool of Chemical TechnologyAalto UniversityEmail: yongdan.li@aalto.fiKemistintie 1, E404
Yongdan Li
Nov-Dec, 2019
After the course the student
• knows the principles of heterogeneous catalysis
• knows the types of homogeneous catalysis and is able to derive rate equations for homogeneous reactions
• recognizes the steps in heterogeneously catalyzed reactions and can derive rate equations based on these steps
• knows the different forms of deactivation of catalysts and can derive reaction rate including deactivation
• is able to evaluate existence of internal and external diffusion limitations in heterogeneously catalyzed reactions
• can calculate size of reactor in the presence of deactivation and mass-transfer limitations
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Course timetableDate/time Place Topic Lecturers
Thu 29 Oct 10-12 L1 (Puu) Lecture 1: Practicalities. Principles of catalysis. Yongdan Li
Wed 30 Oct 12-14 L1 (Puu) Lecture 2: Adsorption and desorption Yongdan Li
Thu 31 Oct 14-16 B 016 (Chem) Ex1: basics, adsorption Tiia Viinikainen, Reetta Karinen
Fri 1 Nov 10-12 L2 (Puu) Lecture 3: Reaction mechanisms I Yongdan Li
Tue 5 Nov 10-12 L1 (Puu) Lecture 4: Reaction mechanisms II Yongdan Li
Thu 7 Nov 12-14 L1 (Puu) Lecture 5: Deactivation I Yongdan Li
Thu 7 Nov 14-16 B016 (Chem) Ex2: Reaction mechanisms Tiia Viinikainen, Reetta Karinen
Fri 8 Nov 10-11 L1 (Puu) Lecture 6: Deactivation II Yongdan Li
Thu 14 Nov 14-16 B016 (Chem) Ex3: Deactivation Tiia Viinikainen, Reetta Karinen
Tue 19 Nov 10-12 L1 (Puu) Lecture 7: Mechanical strength Yongdan Li
Thu 21 Nov 12-14 L1 (Puu) Lecture 8: External diffusion Yongdan Li
Thu 21 Nov 14-16 B016 (Chem) Ex4: Mechanical strength and External diffusion Tiia Viinikainen, Reetta Karinen
Fri 22 Nov 10-12 L1 (Puu) Lecture 9: Internal diffusion Yongdan Li
Tue 26 Nov 10-12 L1 (Puu) Lecture 10: Overall diffusion Yongdan Li
Wes 27 Nov 12-14 L1 (Puu) Lecture 11: Homogeneous catalysis Yongdan Li
Thu 28 Nov 14-16 B016 (Chem) Ex5: Internal and overall diffusions, homogeneous catalysis Reetta Karinen, Tiia Viinikainen
Fri 29 Nov 10-12 L1 (Puu) Lecture 12: Preparing for exam Reetta Karinen, Tiia Viinikainen
Tue 10 Dec 13:00-18:00 A305 (Chem) Exm: final Reetta Karinen, Tiia Viinikainen
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Course structure
Deactivation I
Reaction mechanisms I
Internal diffusion
External diffusion
Reaction mechanisms II
AdsorptionA
A, B
.. . ...
L6
L3
L5
L2
L4
L7
L8
..
Ex1
Ex2
Ex3
Ex4
Ex5
L10: Preparing for the exam
Catalysis
Mechanical strength
L1
Overall diffusion
Deactivation II
L9
L10Homogeneous catalysis L11
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Contact information
• Professor Yongdan Li
Office E404, yongdan.li@aalto.fi
• University lecturer Reetta Karinen
Office E409, reetta.karinen@aalto.fi
• University teacher Tiia Viinikainen
Office E409, tiia.viinikainen@aalto.fi
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MyCourses
MyCourses workspace is used for
- General information and time table
- Lecture slides
- Exercises and their model solutions
- Assignments and return boxes for these
Remember to give feedback!
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Course material
Lectures and exercises
Course book: Fogler, H.S., Elements of chemical reaction engineering, 5th ed., (2016) chapters 10, 14-15, lectures according to this edition
Also valid:
• Fogler, H.S., Elements of chemical reaction engineering, 4th ed., (2006), chapters 10-12, approximately the same topics as in the 5th edition
• Fogler, H.S., Elements of chemical reaction engineering, 3rd ed., (1999), chapters 10-12, approximately the same topics as in the 4th and 5th edition
Check list of errors and their corrections from the book’s web page http://umich.edu/~elements/byconcept/updates/frames.htm
For Chapter 7, 10 published papers are used as references
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Exercises
Exercises have been divided into three category:
A. Pre-exercises
B. Exercises
C. Applied excrcises
A. To be calculated before the exercises using the given hints
B. To be calculated in the exercises using the given hints and with the help of teachers
C. To be calculated using the given hints and the model solutions after the exercises
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Extra points to exam
To encourage learning of calculation skills, extra points to exam will be given on completed exercises
Completed exercises are marked by teachers at the end of each exercise on Thursdays
Total number of exercises this year is 22
A. Pre-exercises: 5
B. Exercises: 10
C. Applied exercises: 7Additional points Number of exercises to be
completed
0.5 p 7
1 p 11
2 p 15
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Assignments
Three assignments need to be accepted to have the right to take the exam!
Assignments and Return boxes in MyCourses
Topic Assistant Published First submission DL Accepted DL
Reaction
mechanisms
Pan Zhengze (zhengze.pan@aalto.fi) Nov 7 Nov 14 Nov 21
Deactivation Tiia Viinikainen
(tiia.viinikainen@aalto.fi)
Nov 14 Nov 21 Nov 28
External diffusion Reetta Karinen
(reetta.karinen@aalto.fi)
Nov 21 Nov 28 Dec 5
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Exam
– 4-5 questions in the exam
– Only material allowed in the exam is handwritten collection of equations
• A4 sheet, on both sides
• Equations with their limitations, symbols with their explanations and units
• Collection of equations needs to be returned in the exam
• Collection of equations may be worth of one additional point (copied collections of equations are not worth the point)
Exams:
December 10 at 13-18
February 19 at 14-19
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Useful
integrals
are given
in the
exam
Old collection of equations
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References for Chapter 3 & 4
1. Reaction kinetics of ethylene combustion in a carbon dioxide stream over a Cu-Mn-O hopcalite catalyst in low temperature range, Industrial & Engineering Chemistry Research, 52 (2013) 686-691
2. A carbon in molten carbonate anode model for a direct carbon fuel cell, Electrochimica Acta, 55 (2010) 1958-1965
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References for Chapter 7
1. Effect of abnormal treatment on the mechanical strength of iron-based high-temperature shift catalyst, Applied Catalysis A-General 133 (1995) 293-304
2. Optimizing the mechanical strength of Fe-based commercial high-temperature water-gas shift catalyst in a reduction process, Industrial & Engineering Chemistry Research 35 (1996) 4050-4057
3. Effect of the mechanical failure of catalyst pellets on the pressure drop of a reactor, Chemical Engineering Science, 58 2003 3995 4004
4. Effects of the calcination conditions on the mechanical properties of a PCoMo/Al2O3 hydrotreating catalyst, Chemical Engineering Science, 57 (2002) 3495 3504
5. Effect of the number of testing specimens and the estimation methods on the Weibull modulus of solid catalysts, Chemical Engineering Science, 56 (24) (2001)7035 7044
6. Measurement and statistics of single pellet mechanical strength of differently shaped catalysts, Powder Technology, 113 (2000) 176 184
7. Understandings on the scattering property of the mechanical strength data of solid catalysts: A statistical analysis of iron based high temperature water gas shift catalysts, Catalysis Today, 51(1) (1999) 73-84
8. Mechanical strength of solid catalysts: Recent developments and future prospects, AIChE Journal 53 (2007) 2618-2629
9. Mechanical Stability of Monolithic Catalysts: Factors Affecting Washcoat Adhesion and Cohesion During Preparation, AICHE Journal 60 (2014) 2765-2773
10. Particle size effect on the catalyst attrition in a lab-scale fluidized bed, AICHE journal 63 (2017) 914-920
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Catalysis Basics
Catalysis
Exists as an important natural phenomenon
➢ In natural evolution, catalysis played a
key role in creating the biosphere
Gives birth to pillar techs in modern life
➢ Microbial-enzyme applications enable
delicious foods: bread, beer and wine
➢ Sulfuric acid production was called as the
mother of modern chemical industry
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Definition of a Catalyst
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A catalyst is a substance that increases the rate at which a chemical
reaction approaches equilibrium without itself becoming permanently
involved in the reaction
1925
Active site
H.S. Taylor
1900 1900
Instable Intermediate
F.W. Ostwald P. Sabatier
M. Che: Presented on the “Workshop for Building up the Core Courses in Industrial Catalysis”, Tianjin, August, 2005
A physical effect
J.T. Richardson, Principles of Catalyst Development, Plenum Press, NewYork NY, 1989
Catalytic Reaction Pathway
Reaction Euncat (kJ/mol) Ecat (kJ/mol) catalyst
2 HI → H2 + I2 184 105 or 59 Au or Pt
2 N2O → 2 N2 + O2 245 121 or 134 Au or Pt
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Four Key Points
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1. Chemical equilibrium cannot be changed
2. The catalyst accelerates forward and backward reactions
3. A catalyst has selectivity
4. A catalyst has limited life
Depends only on the start and end states of system
Accelerates the reactions with Gr<0
In the same time and with the same ratio
Chemical equilibrium constant is not changed Kp = k+ / k-
Accelerate one specific reaction
Deactivation is a slow process
Lose activity for many reasons, e.g. carbon deposition, poisoning.
Sub-disciplines of Catalysis
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Homogeneous catalysis
➢ Happens via complexing and rearrangement steps
➢ Has high specific activity and selectivity
Heterogeneous catalysis
➢ Mechanism: surface adsorption and reaction
➢ Ease catalyst separation from reactants
➢ More suitable for large scale production
Enzymatic catalysis
➢ Bioprocess based on bioactive material
Role of Catalysis in Chemical Manufacture
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All Chemical Processes Catalytic Processes
G. Rothenberg, Catalysis: Concepts and Green Applications, Wiley-VCH, 2008
Multiscale-multidisciplinary Nature
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Chemical Process Technology
Intrinsic processKinetics, selectivity,
Mass, heat and
momentum transfer,
Stability and life
Supporting knowledgeSynthetic chemistry, Engineering sciences, Catalysis,
Transfer, Interface, Physics and Materials science
Application
New process
Max yield
Min consumption
Ease operation
Active sitesMaterial, structure,
Mechanism
Microscopic dynamics
ParticleShape, size, pores,
Mechanical property
ReactorReaction engineering,
Optimization,
Mass and heat transfer
How Catalytic Science Supports
Humanity
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Ammonia Synthesis-Food
Oil Refining-Energy
Automotive Emission Control-Air
Milestones of Catalysis Application in the 20th Century
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Ammonia: The key molecule to sustaining a growing world population
Ammonia and its compounds, primarily ammonium nitrate and other ammonium salts, replenishnitrogen in depleted soils. Without artificial fertilizer there would not be enough food forthe growing world population.
M.Appl. “Ammonia”, Wiley-VCH (1999)
Ammonia Synthesis
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Fritz Haber discovereda catalyst to makeammonia from nitrogenand hydrogen (1908)
Although the atmosphere consists of about 79 % nitrogen, no one knew how to
convert it into ammonia on an industrial scale.
Chemistry Nobel Prize, 1918
N2 + 3H2 2NH3
Activation energy for gas phase reaction as high as 1129 kJ/mole
Until —
Ammonia Synthesis
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In 1913, Carl Bosch made the process practical on large scale based on a fusediron catalyst discovered by Alwin Mittasch.
Chemistry Nobel Prize, 1931 Commercialization
Modern ammonia synthesis reactor- Kellogg
Ammonia Synthesis
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✓ Adsorption of nitrogen is the rate limiting step with an activation energy of ~21 kJ/mole.
✓ At 500 oC increases the reaction rate by 1013 times!
Gerhard Ertl
Chemistry Nobel Prize 2007
Mechanism of catalytic ammonia synthesis
G. Ertl. Catal. Rev. Sci. Eng. 21 (1980), 201
Ammonia Synthesis
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July 26, 1943, Los Angeles, California: A smog so sudden and severe that "Los
Angeles residents believe the Japanese are attacking them with chemical warfare."
Los Angeles smog
Automotive Emission Control
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United States federal emission
standards for heavy-duty diesel engines
Los Angeles
Catalysis makes a clean world
0 1 2 3 4 5 60.000
0.025
0.050
0.075
0.100
0.125
0.150
EPA98
EPA04
EPA07EPA10
Particulates (g/bhp-hr)
-94% NOx (g/bhp-hr)
-90
%
American Clean Air Act 1963
Extension 1970 1977 1990
Automotive Emission Control
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Three way catalyst (TWC) for gasoline powered cars
TWCJ. Wang et al. Catalysis Reviews: Science and Engineering 57 (2015), 79–144
Active site: Pd Pt Rh
γ-Al2O3
Cordierite
N2
CO2
H2O
N2
H2O
NO
CO
HC
(Life:120000 mile)Pressure drop limitations lead to new reactor design
Early installation: Packed bedMonolithic reactor
CeO2-ZrO2
Automotive Emission Control
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Operating
window
A/F≈14.6
More powerful engine
Higher fuel efficiency
Three-way catalyst
Lean-burn
Gasoline engine
(A/F≥20)
Diesel engine
(A/F≥17.5)
Automotive Emission Control
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➢ NOx Storage and Reduction (NSR), also called Lean NOx Trap (LNT)
Light-duty diesel powered car Martin Winterkorn (CEO of Volkswagen)
Complex engine control
Passive NOx removal
➢ Selective Catalytic Reduction by NH3 (NH3-SCR)Active NOx removal
High fixed investment
Big installation space
D.W. Fickel et al. Applied Catalysis B: Environmental 102 (2011) 441–448
Heavy-duty diesel powered truck Urea solution storage tank
Automotive Emission Control
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Simplified process scheme of an oil refinery
1-Hydrotreating
2-Cracking
1
2
3
3-Reforming
I. Chorkendorff and J.W. Niemantsverdriet, Concepts of Modern Catalysis and Kinetics, Wiley-VCH, 2003 & 2007
Oil Refining
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Hydrotreating
Cracking
Reforming
HDS, HDO, HDN, HDA
C16H34→C8H18+C8H16
Amorphous silica-aluminas and zeolites
n-C5H12→i-C5H12, C6H14→C6H6
Bifunctional catalysts, Pt-Re/Al2O3, Pt-Ir/Al2O3
Co-MoS2/Al2O3, Ni-WS2/Al2O3, Ni-MoS2/Al2O3
Oil Refining
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Catalytic cracking Heavier fractions are converted into naphtha and middle distillates
AlCl3
Earthly 20th century
Acid-treated clay
1930 1940
silica-alumina Zeolites
1963-Nowadays
Catalyst
20% Zeolite Y
80% Matrix
Circulating fluidized-bed reactor
Oil Refining
37 E.T.C. Vogt and B.M. Weckhuysen, Chemical Society Reviews, 44 (2015) 7342-7370
Oil Refining
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Year Process Catalyst
1750 H2SO4 lead chamber process NO/NO2
1870 SO2 oxidation Pt
1880 Deacon process(Cl2 from HCl) ZnCl2-CuCl2
1885 Claus process(H2S and SO2 to S) bauxite
1900 fat hydrogenation Ni
methane from syngas
1910 coal Liquefaction Fe
upgrading coal liquids WS2
ammonia synthesis (Haber-Bosch) Fe/K
NH3 oxidation to nitric acid Pt
Historical Overview of Catalytic Technology
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1920 methanol synthesis (high pressure process) Zn, Cr oxide
Fischer-Tropsch synthesis promoted Fe, Co
SO2 oxidation V2O5
acetaldehyde from acetylene Hg2+/H2SO4
1930 catalytic cracking (fixed bed, Houdry) clays
Ethane epoxidation Ag
polyethylene chloride Peroxide
Polyethylene (low density, ICI)
oxidation of benzene to maleic anhydride V
alkylation HF/H2SO4
Historical Overview of Catalytic Technology
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1940 hydroformylation, alkene to aldehyde Co
catalytic reforming(gasoline) Pt
cyclohexane oxidation(nylon 66 production) Co
benzene hydrogenation to cyclohexane Ni, Pt
Synthetic rubber, SBR
BNR
Butylrubber
Li, peroxide
peroxide
Al
1950 polyethylene (high density) Ziegler-Natta
Phillips
Ti
Cr
polypropene Ziegler-Natta Ti
polybutadiene Ziegler-Natta Ti, Co, Ni
hydrodesulfiding (HDS) Co, Mo sulfides
naphtalene oxidation to phthalic anhydride V, Mo oxides
ethylene oxidation to acetaldehyde Pd, Cu
p-xylene oxidation to terephtalic acide Co, Mn
ethylene oligomerization Al(Et)3
Historical Overview of Catalytic Technology
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1960 butene oxidation to maleic anhydride V, P oxides
acrylonitrile via ammoxidation of propene (Sohio) Bi, Mo oxides
propene oxidation to acrolein/acrylic acid Bi, Mo oxides
xylenes hydroisomerisation Pt
propene metathesis W, Mo, Re
adiponitrile via butadiene hydrocyanization Ni
improved reforming catalysts Pt, Re/Al2O3
improved cracking catalysts Zeolites
acetic acid from MeOH (carbonylation) Co
vinyl chloride via ethene oxyclorination Cu chloride
ethene oxidation to vinyl acetate Pd/Cu
o-xylene oxidation to phthalic anhydride V, Ti oxides
propene oxidation to propene oxide Mo
hydrocracking Ni-W/Al2O3
HT water-gas shift process Fe2O3/Cr2O3/MgO
LT water-gas shift process CuO/ZnO/Al2O3
Historical Overview of Catalytic Technology
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Historical Overview of Catalytic Technology
1970 methanol synthesis (low pressure, ICI) Cu-Zn-Al oxide
acetic acid from MeOH (carbonylation, low pressure
process, Monsanto)
Rh
improved process for xylene isomerization zeolite
-alkenes via ethene
oligomerization/isomerization/metathesis (SHOP)
Ni, Mo
improved hydroformylation Rh
auto exhaust gas catalysts Pt/Rh
L-DOPA(Monsanto) Rh
cyclooctenamer(metathesis) W
hydroisomerization Pt/zeolite
selective reduction of NO(with NH3) V2O5/TiO2
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Historical Overview of Catalytic Technology
1980 gasoline from methanol process (Mobil) zeolite
vinyl acetate from ethane and acetic acid Pd
methylacetate (carboxylation) Rh
methylacrylate via t-butanol oxidation Mo oxides
improved coal liquefication Co, Mo sulfides
diesel fuel from syngas K, Na
1990 polyketon (from CO and ethene Pd
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Home Work (Optional)
◼ Select 3 catalytic processes in the table and collect information on
the www and summarize:
1. Describe the process and the catalysts used in history
2. Describe the evolement of the reactor types used in history
3. Describe the scale up of the process along history
4. Descibe the present scale of production and the contribution
to the humanity nowadays
Catalysis Reaction Engineering
Yongdan Li
Nov-Dec, 2019
Professor of Industrial ChemistryDepartment of Chemical and Metallurgical EngineeringSchool of Chemical TechnologyAalto UniversityEmail: yongdan.li@aalto.fiKemistintie 1, E404