1. Dasar2 Katalisis pada industri teknik

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1. Catalysis Basics

2. 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
motherof modern chemicalindustry
15

3. Definition of a Catalyst
16
Acatalystisasubstancethatincreasestherateatwhichachemical
reactionapproachesequilibriumwithoutitselfbecomingpermanently
involvedinthereaction
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 physicaleffect
J.T. Richardson, Principles of Catalyst Development, Plenum Press, NewYorkNY, 1989

4. CatalyticReactionPathway
Reaction E
uncat(kJ/mol) E
cat(kJ/mol) catalyst
2 HI H
2+ I
2 184 105 or 59 Au or Pt
2 N
2O 2 N
2+ O
2 245 121 or 134 Au or Pt
17

5. Four Key Points
18
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 G
r<0
In the same time and with the same ratio
Chemical equilibrium constant is not changedK
p= k
+/ k
-
Accelerate one specific reaction
Deactivation is a slow process
Lose activity for many reasons, e.g.carbon deposition, poisoning.

6. Sub-disciplines of Catalysis
19
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 suitablefor large scale production
Enzymatic catalysis
Bioprocess based on bioactive material

7. Role of Catalysis in Chemical Manufacture
20
All Chemical ProcessesCatalytic Processes
G. Rothenberg, Catalysis: Concepts and Green Applications, Wiley-VCH, 2008

8. Multiscale-multidisciplinary Nature
21
Chemical Process Technology
Intrinsic process
Kinetics, selectivity,
Mass, heat and
momentum transfer,
Stability and life
Supporting knowledge
Synthetic chemistry, Engineering sciences, Catalysis,
Transfer, Interface, Physics and Materials science
Application
New process
Max yield
Min consumption
Ease operation
Active sites
Material, structure,
Mechanism
Microscopic dynamics
Particle
Shape, size, pores,
Mechanical property
Reactor
Reaction engineering,
Optimization,
Mass and heat transfer

9. How Catalytic Science Supports
Humanity

10. 23
Ammonia Synthesis-Food
Oil Refining-Energy
Automotive Emission Control-Air
Milestones of Catalysis Application in the 20th Century

11. 24
Ammonia: The key molecule to sustaining a growing world population
Ammoniaanditscompounds,primarilyammoniumnitrateandotherammoniumsalts,replenish
nitrogenindepletedsoils.Withoutartificialfertilizertherewouldnotbeenoughfoodfor
thegrowingworldpopulation.
M.Appl. “Ammonia”, Wiley-VCH (1999)
Ammonia Synthesis

12. 25
FritzHaberdiscovered
acatalysttomake
ammoniafromnitrogen
andhydrogen(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
N
2＋3H
22NH
3
Activation energy for gas phase reaction as high as 1129 kJ/mole
Until —
Ammonia Synthesis

13. 26
In1913,CarlBoschmadetheprocesspracticalonlargescalebasedonafused
ironcatalystdiscoveredbyAlwinMittasch.
ChemistryNobelPrize,1931 Commercialization
Modern ammonia synthesis reactor-Kellogg
Ammonia Synthesis

14. 27
Adsorption of nitrogen is the rate limiting step with an activation energy of ~21 kJ/mole.
At 500
o
Cincreases the reaction rate by 10
13
times！
Gerhard Ertl
Chemistry Nobel Prize 2007
Mechanism of catalytic ammonia synthesis
G. Ertl. Catal. Rev. Sci. Eng. 21 (1980), 201
Ammonia Synthesis

15. 28
July26,1943,LosAngeles,California:Asmogsosuddenandseverethat"Los
AngelesresidentsbelievetheJapaneseareattackingthemwithchemicalwarfare."
Los Angeles smog
Automotive Emission Control

16. 29
United States federal emission
standards for heavy-duty diesel engines
Los Angeles
Catalysis makes a cleanworld0 1 2 3 4 5 6
0.000
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

17. 30
Three way catalyst (TWC) for gasoline powered cars
TWC
J. Wang et al. Catalysis Reviews: Science and Engineering 57 (2015), 79–144
Active site: PdPt Rh
γ-Al
2O
3
Cordierite
N
2
CO
2
H
2O
N
2
H
2O
NO
CO
HC
(Life:120000 mile)
Pressure drop limitations lead to new reactordesign
Early installation: Packed bed
Monolithic reactor
CeO
2-ZrO
2
Automotive Emission Control

18. 31
Operating
window
A/F≈14.6
More powerful engine
Higherfuelefficiency
Three-way catalyst
Lean-burn
Gasoline engine
（A/F≥20）
Diesel engine
（A/F≥17.5）
Automotive Emission Control

19. 32
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 NOxremoval
Selective Catalytic Reduction by NH
3(NH3-SCR)
Active NOxremoval
High fixed investment
Big installation space
D.W. Fickel et al. Applied Catalysis B: Environmental 102 (2011) 441–448
Heavy-duty diesel powered truckUrea solution storage tank
Automotive Emission Control

20. 33
Simplified process scheme of an oil refinery
1-Hydrotreating
2-Cracking
1
2
3
3-Reforming
I. Chorkendorffand J.W. Niemantsverdriet, Concepts of Modern Catalysis and Kinetics, Wiley-VCH, 2003 & 2007
Oil Refining

21. 34
Hydrotreating
Cracking
Reforming
HDS, HDO, HDN, HDA
C16H34→C8H18+C8H16
Amorphous silica-aluminasand 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

22. 35
Catalytic crackingHeavier fractions are converted into naphtha and middle distillates
AlCl3
Earthly 20
th
century
Acid-treated clay
1930 1940
silica-alumina Zeolites
1963-Nowadays
Catalyst
20%ZeoliteY
80%Matrix
Circulating fluidized-bed reactor
Oil Refining

23. 36
E.T.C. Vogt and B.M. Weckhuysen, Chemical Society Reviews, 44 (2015) 7342-7370
Oil Refining

24. 37
Year Process Catalyst
1750 H
2
SO
4
lead chamber process NO/NO
2
1870 SO
2
oxidation Pt
1880 Deacon process(Cl
2
from HCl) ZnCl
2
-CuCl
2
1885 Claus process(H
2
S and SO
2
to S) bauxite
1900 fat hydrogenation Ni
methane from syngas
1910 coal Liquefaction Fe
upgrading coal liquids WS
2
ammonia synthesis (Haber-Bosch) Fe/K
NH
3
oxidation to nitric acid Pt
Historical Overview of Catalytic Technology

25. 38
1920 methanol synthesis (high pressure process)Zn, Cr oxide
Fischer-Tropschsynthesis promoted Fe, Co
SO
2
oxidation V
2
O
5
acetaldehyde from acetylene Hg
2+
/H
2
SO
4
1930 catalytic cracking (fixed bed, Houdry) clays
Ethane epoxidation Ag
polyethylene chloride Peroxide
Polyethylene (low density, ICI)
oxidation of benzene to maleic anhydrideV
alkylation HF/H
2
SO
4
Historical Overview of Catalytic Technology

26. 39
1940hydroformylation, alkene to aldehydeCo
catalytic reforming(gasoline) Pt
cyclohexane oxidation(nylon 66 production)Co
benzene hydrogenation to cyclohexaneNi, Pt
Synthetic rubber, SBR
BNR
Butylrubber
Li, peroxide
peroxide
Al
1950polyethylene (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 anhydrideV, Mo oxides
ethylene oxidation to acetaldehyde Pd, Cu
p-xylene oxidation to terephtalic acideCo, Mn
ethylene oligomerization Al(Et)
3
Historical Overview of Catalytic Technology

27. 40
1960buteneoxidation to maleic anhydride V, P oxides
acrylonitrile via ammoxidationof propene (Sohio)Bi, Mo oxides
propene oxidation to acrolein/acrylic acid Bi, Mo oxides
xylenes hydroisomerisation Pt
propene metathesis W, Mo, Re
adiponitrilevia butadiene hydrocyanization Ni
improved reforming catalysts Pt, Re/Al
2
O
3
improved cracking catalysts Zeolites
acetic acid from MeOH(carbonylation) Co
vinyl chloride via ethene oxyclorinationCu chloride
ethene oxidation to vinyl acetate Pd/Cu
o-xylene oxidation to phthalic anhydrideV, Tioxides
propene oxidation to propene oxide Mo
hydrocracking Ni-W/Al
2
O
3
HT water-gas shift process Fe
2
O
3
/Cr
2
O
3
/MgO
LT water-gas shift process CuO/ZnO/Al
2
O
3
Historical Overview of Catalytic Technology

28. 41
Historical Overview of Catalytic Technology
1970methanol 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) V
2
O
5
/TiO
2

29. 42
Historical Overview of Catalytic Technology
1980gasoline from methanol process (Mobil) zeolite
vinyl acetate from ethane and acetic acidPd
methylacetate(carboxylation) Rh
methylacrylate via t-butanol oxidation Mo oxides
improved coal liquefication Co, Mo sulfides
diesel fuel from syngas K, Na
1990polyketon (from CO and ethene Pd

30. 43
Home Work (Optional)
Select 3 catalytic processes in the table and collect information on
the www and summarize:
1.Describetheprocessand thecatalystsusedin history
2.Describetheevolementof thereactortypesusedin history
3.Describethescaleupof theprocessalonghistory
4.Descibethepresentscaleof productionand thecontribution
to thehumanitynowadays

31. Catalysis
Reaction Engineering
YongdanLi
Nov-Dec, 2018
Professorof Industrial Chemistry
Department of Chemicaland MetallurgicalEngineering
School of Chemical Technology
Aalto University
Email: [email protected]
Kemistintie1, E404