catalytic reaction engineering - aalto

CatalyticReaction Engineering

Professor of Industrial ChemistryDepartment of Chemical and Metallurgical EngineeringSchool of Chemical TechnologyAalto UniversityEmail: [email protected] 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

2

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

3

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

4

Contact information

• Professor Yongdan Li

Office E404, [email protected]

• University lecturer Reetta Karinen


• University teacher Tiia Viinikainen


5

mailto:[email protected]



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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http://umich.edu/~elements/byconcept/updates/frames.htm

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

8

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

9

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 ([email protected]) Nov 7 Nov 14 Nov 21

Deactivation Tiia Viinikainen

([email protected])

Nov 14 Nov 21 Nov 28

External diffusion Reetta Karinen

([email protected])

Nov 21 Nov 28 Dec 5

10

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

11

Useful

integrals

are given

in the

exam

Old collection of equations

12

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

13

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

16

Definition of a Catalyst

17

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

20

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

21

All Chemical Processes Catalytic Processes

G. Rothenberg, Catalysis: Concepts and Green Applications, Wiley-VCH, 2008

Multiscale-multidisciplinary Nature

22

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

24

Ammonia Synthesis-Food

Oil Refining-Energy

Automotive Emission Control-Air

Milestones of Catalysis Application in the 20th Century

25

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

26

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

27

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

29

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

30

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


31

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


32

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）


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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


34

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

35

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

36

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

39

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


40

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


41

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


42


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

43


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

44

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: [email protected] 1, E404

catalytic reaction engineering - aalto

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