cbe 40445 lecture 15 introduction to catalysis

W. F. Schneider CBE 40445

CBE 40445Lecture 15

Introduction to Catalysis

Developed by Prof. Schneider1,2

Modified by Prof. Hicks1

1Department of Chemical and Biomolecular Engineering

2Department of Chemistry and BiochemistryUniversity of Notre Dame

Fall 2011

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

Importance of Catalysts


Bartholomew and Farrauto, Fundamentals of Industrial Catalytic Processes, Wiley, 2006.

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


What is a “Catalyst”

A catalyst (Greek: καταλύτης, catalytēs) is a substance that accelerates the rate of a chemical reaction without itself being transformed or consumed by the reaction. (thank you Wikipedia)

A + B

C

ΔG

Ea

uncatalyzed

A + B +catalyst

C + catalyst

ΔG

Ea′

catalyzed

k(T) = k0e-Ea/RT

Ea′ < Ea

k0′ > k0

k′ > k

ΔG = ΔG

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Catalysts Open Up New Reaction Pathways

CH3

C

CH3

O

CH2

C

CH3

OH

propanone propenol

H2C

H O

CCH3

‡

‡

propanone

propenol

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○



CH3

C

CH3

O

CH2

C

CH3

OH

propanone propenol

OH−CH2

C

CH3

O−

+ H2O

−OH−

Base catalyzed

propanone

propenol

intermediate

‡ ‡

rate = k[OH−][acetone]

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○



CH3

C

CH3

O

CH2

C

CH3

OHpropanone

propenol

+ H2O

Acid catalyzed

H3O+

CH3

C

CH3

OH

+

−H3O+

propenol

differentintermediate

‡ ‡

propanone

rate = k[H3O+][acetone]

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Types of Catalysts - Enzymes

The “Gold Standard” of catalysts

Highly specificHighly selectiveHighly efficientCatalyze very difficult

reactionsN2 NH3

CO2 + H2O C6H12O6

Works better in a cell than in a 100000 l reactor

Triosephosphateisomerase

“TIM”Cytochrome C Oxidase

Highly tailored “active sites”Often contain metal atoms

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Types of Catalysts – Organometallic Complexes

Perhaps closest man has come to mimicking nature’s success

2005 Noble Prize in Chemistry

Well-defined, metal-based active sites

Selective, efficient manipulation of organic functional groups

Various forms, especially for polymerization catalysis

Difficult to generalize beyond organic transformations

Polymerization:

Termination:

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Types of Catalysts – Homogeneous vs. Heterogeneous

Homogeneous catalysisSingle phase

(Typically liquid)Low temperature

Separations are tricky

Heterogeneous catalysisMultiphase

(Mostly solid-liquid and solid-gas)High temperature

Design and optimization tricky

Zeolite catalyst Catalyst powders

Newer area of Research: Tethered Catalysts (maintaining

selectivity of homogeneous catalysts but tethered to a solid support)

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Types of Catalysts: Crystalline Microporous Catalysts

Regular crystalline structure Porous on the scale of molecular dimensions

3 – 20 Å (microporous), 20-500 Å (mesoporous) Up to 1000’s m2/g surface area

Catalysis through shape selection acidity/basicity incorporation of metal particles

Used as supports for other metal precursors

10 Å 40 Å

Zeolite (silica-aluminate)Silico-titanate

MCM-41 (mesoporous silica)

Applied Catalysis A, 2009, 360, 59-65.

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

What are zeolites ?- Aluminosilicates- microporous ( pores < 20Å)- Crystalline- Framework of AlO4 and SiO4 Td-units (tetrahedral)- Possess ordered pore systems- Acidity arises from incorporation of Al

Types of Catalysts: Zeolites

Morphology changes due to additives, quantities, pH, time, etc. Shown below are SEM images of HZSM-5 (5.6 Å pores)

Neumann and Hicks, 2011.

All silica ~ weak acidity SiO2/Al2O3 ~ Brønsted acidity

Al2O3 source

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

Sodalite(SOD)pores ~3Å

Zeolite - A(LTA)pores ~ 4Å

Zeolite - X, Y(FAU)pores ~ 7.4ÅA large cage (~ 12Å)

formed in A and X,Y

[SiO4 ]4- [AlO4]5-

-cagesLTA FAU

Types of Catalysts: Zeolites

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Types of Catalysts: Amorphous Heterogeneous Catalysts

Amorphous, high surface area supports Alumina, silica, activated carbon, … Up to 100’s of m2/g of surface area

Impregnated with catalytic transition metals Pt, Pd, Ni, Fe, Ru, Cu, Ru, …

Typically pelletized or on monoliths Cheap, high stability, catalyze many types of reactions Most used, least well understood of all classes

SEM micrographs of alumina and Pt/alumina

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

Types of Catalysts: Motivation for Tethered Catalysts

Traditional Heterogeneous (Insoluble)

Easy to separate Multiple types of active

sites Less mobility / spatially

constricted Diffusion effects

Homogeneous (Soluble) High mobility - active Single type of active

site -selective Control of

stereochemistry Difficult to separate

Tethered• Insoluble• Single type of active

site-selective• Easy to separate

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

Types of Catalysts: Examples of Tethered Catalysts


N

OO

OV

OO

HN

O

SiO O

OMe

O O

SiOSiMe3

NSi Zr

Cl

Cl

OSi

Hicks, J. C.; Dabestani, R.; Buchanan III, A. C.; Jones, C. W., Inorg. Chim. Acta, 2008.

R. A. Shiels, K. Venkatasubbaiah and C. W. Jones, Adv. Synth. Catal. (2008) 350, 2823-2834.

Zr

SiO O

Si

O

Si

S

F3CFF

F

O

O

O

Al Al

H2C

Me

J. C. Hicks, B. A. Mullis and C. W. Jones,J. Am. Chem. Soc. (2007) 129, 8426-8427.

Collaboration between Hicks and Schneider Groups

O

SiO2

Si

NH2

OMe

OMe

Hicks, J. C.; Jones, C. W., Langmuir 2006, 22, 2676.Hicks, J. C.; Dabestani, R.; Buchanan III, A. C.; Jones, C. W., Chem. Mater. 2006, 18, 5022.

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Important Heterogeneous Catalytic Processes

Haber-Bosch process N2 + 3 H2 → 2 NH3

Fe/Ru catalysts, high pressure and temperature Critical for fertilizer and nitric acid production

Fischer-Tropsch chemistry n CO + 2n H2 → (CH2)n + n H2O , syn gas to liquid fuels Fe/Co catalysts Source of fuel for Axis in WWII

Fluidized catalytic cracking High MW petroleum → low MW fuels, like gasoline Zeolite catalysts, high temperature combustor In your fuel tank!

Automotive three-way catalysis NOx/CO/HC → H2O/CO2/H2O Pt/Rh/Pd supported on ceria/alumina Makes exhaust 99% cleaner

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Heterogeneous Catalytic Reactors

Design goals rapid and intimate contact

between catalyst and reactants

ease of separation of products from catalyst

Packed Bed(single or multi-tube)

SlurryReactor

FluidizedBed

CatalystRecycleReactor

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

FCC: Fluidized Catalytic Cracker


Gasoline Production

Gas oil enters the riser reactor and is mixed with a zeolite catalyst (Zeolite Y).

Acid-catalyzed cracking reactions occur in reactor.

Coke formation occurs quickly on the catalyst (carbon deposition).

Catalyst residence time is ~ 1.5 seconds.

Catalyst is separated, regenerated, and re-injected.

Bartholomew and Farrauto, Fundamentals of Industrial Catalytic Processes, Wiley, 2006.

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Automotive Emissions Control System

“Three-way” CatalystCO CO2

HC CO2 + H2ONOx N2

Pt, Rh, PdAlumina, ceria, zirconia, …

Most widely deployed heterogeneous catalyst in the world – you probably own one!

Monolith reactor

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Length Scales in Heterogeneous Catalysis

Mass transport/diffusion Chemical adsorption and reaction

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

Steps in a Heterogeneous Catalytic Reactor


Diffusion Steps: 1, 2, 6, 7.Reaction Steps: 3, 4, 5.

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Characteristics of Heterogeneous Supported Catalysts

Surface area: Amount of internal support surface accessible to a fluid Measured by gas adsorption isotherms

Loading: Mass of transition metal per mass of support

Dispersion: Percent of metal atoms accessible to a fluid

support

M M M

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Rates of Catalytic Reactions

Pseudo-homogeneous reaction rate r = moles / volume · time

Mass-based rate r′ = moles / masscat · time r′ = r / ρcat

Heterogeneous reactions happen at surfaces Area-based rate

r′′ = moles / areacat · time r′′ = r′ / SA, SA = area / mass

Heterogeneous reactions happen at active sites Active site-based rate

Turn-over frequency TOF = moles / site · time TOF = r′′ / ρsite

TOF (s−1)Hetero. cats. ~101

Enzymes ~106

TOF (s−1)Hetero. cats. ~101

Enzymes ~106

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Adsorption and Reaction at Solid Surfaces

Physisorption: weak van der Waals attraction of a fluid (like N2 gas) for any surface Eads ~10 – 40 kJ/mol

Low temperature phenomenon Exploited in measuring gross surface area

Chemisorption: chemical bond formation between a fluid molecule (like CO or ethylene) and a surface site Eads ~ 100 – 500 kJ/mol

Essential element of catalytic activity Exploited in measuring catalytically active sites

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Comparing Physi- and Chemisorption on MgO(001)

1.77

1.51

2.10

2.60

CO2

SO2

Physisorbed CO2

-2 kcal mol-1 GGA

Chemisorbed SO2

(“sulfite”)-25 kcal mol-1 GGA

SO3Chemisorbed SO3

(“sulfate”)-50 kcal mol-1 GGA

1.66

1.481.45

2.12

2.58

MgO(001) supercell

1.48

1.25

Mg

O

:O:surf

::

2-

COO

:O:surf:

:2-

SOO :

:O:surf

::

2-

SOO

O

Schneider, Li, and Hass, J. Phys. Chem. B 2001, 105, 6972

Calculated from first-principles DFT

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Measuring Concentrations in Heterogeneous Reactions Kinetics

Fluid concentrations Traditionally reported as pressures (torr, atm, bar) Ideal gas assumption: Pj = Cj RT

Surface concentrations “Coverage” per unit area

nj = molesj / area

Maximum coverage called monolayer1 ML: nj,max = ~ 1015 molecules / cm2

Fractional coverageθj = nj / nj,max

0 ≤ θj ≤ 1

θj = 1/5

Rate = f(Pj,θj)

Metal particle surface

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Adsorption Isotherms

Molecules in gas and surface are in dynamic equilibrium

A (g) + M (surface) ↔ M-A Isotherm describes pressure dependence of equilibrium

Langmuir isotherm proposed by Irving Langmuir, GE, 1915 (1932 Noble Prize) Adsorption saturates at 1 monolayer All sites are equivalent Adsorption is independent of coverage

Site conservationθA + θ* = 1 +

Equilibriumrateads = ratedes

AA a d

A

,1

KPK k k

KP

*a a Arate k P N d d Arate k N

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Using the Langmuir Isotherm

Example: CO adsorption on 10% Ru/Al2O3 @ 100°CPCO (torr) 100 150 200 250 300 400

COads (μmol/gcat) 1.28 1.63 1.77 1.94 2.06 2.21

100 200 300 4000.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4

2.6

Pressure (torr)

n CO ( m

ol/g cat)

CO adsorption on Ru/Al2O

3 at 100C

Non-linear regression

100 200 300 40050

100

150

200

Pressure (torr)

PC

O/nC

O (to

rr g c

at/

mol)

CO adsorption on Ru/Al2O

3 at 100C

Linearized model

nCO,∞ = 2.89 μmol/gcat

K = 0.0082

CO, COCO

CO1

n KPn

KP

CO CO

CO CO, CO,

1P P

n n Kn

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○


Brunauer-Emmett-Teller Isotherm (BET)

Solid Surface

ΔHads

ΔHcond

ΔHads/ΔHcond

ads cond

mono

( )

vap

(1 )(1 (1 ) )

,H H

RT

czVV z c z

Pz c eP

Relaxes Langmuir restriction to single layer adsorption Monolayer adsorption; multilayer condensation

Useful for total surface area measurement Adsorption of boiling N2 (78 K)

cbe 40445 lecture 15 introduction to catalysis

Documents

tethered catalysts

types of catalysts homogeneous

chemical reaction

metal precursors10

metal atomscbe

solid supportcbe

crystalline framework

active sitesoften