ChE 511 - Catalysis

Prof. Dr. Ik nal

CATALYSTS Used in Chemical and Allied Industries. Approximately 1/3 of Material GNP of U.S. involves a catalytic process somewhere between raw materials and finished products. TYPES OF CATALYTIC PROCESSES Homogeneous : Catalyst is in a solution with at least one of the reactants. Heterogeneous : Involves more than one phase where usually catalyst is in solid phase and reactants and products are gases or liquids.

MOST IMPORTANT FUNCTIONS OF A CATALYST Activity Selectivity Long-term stability

ChE 511 - Catalysis

Prof. Dr. Ik nal

LECTURE-1
Thermo. Fluid Flow Mathematics Design Economics

Chemical Kinetics

Chemical Reactor

Design of a chemical reactor

Chemical Process

Product Marketing

Mass Transfer

Heat Transfer

Materials

Process Control

Bench-scale Batch Reactor

Bench-scale Continuous Reactor

Pilot Plant

Demonstration Plant----Operating Plant

ChE311

ChE 511 - Catalysis

Prof. Dr. Ik nal

ChE 511 - Catalysis

Prof. Dr. Ik nal

LECTURE-1

ChE311

ChE 511 - Catalysis

Prof. Dr. Ik nal

LECTURE-1 Typical Plant Capacity Price Tons/yr $/1b ___________________ _______ 6 8 Petroleum Refining 10 - 10 0.1 Commodity Chemicals 104 106 0.1-2 Fine Chemicals 102 104 2 10 Foods Materials 0- 3 Pharmaceuticals 10 - 10 Very different tasks in each category for a Ch.E. Important In petroleum + commodity Fine chemicals Foods & pharmaceuticals Low-cost Patent protection Patents, trademarks Marketing, advertising Category Waste Products lb/lb 0.1 1-3 2 10 1 50

ChE311

ChE 511 - Catalysis

Prof. Dr. Ik nal

PROCESS NEED New Process Modification of Old Process

DEFINE PROBLEM/OBJECTIVES

PROCESS ENGINEERING Comparison with Similar Processes

Activity Selectivity Deactivation Regeneration Cost Availability

CHEMICAL ENGINEERING Chemical Diffusional Mechanical Process Analysis Reaction Engineering Economics

CATALYST RESEARCH Catalyst Prop. Catalytic Mech. Catalyst Rate Equation Support Reaction Steps Promoters Energetics Preparation Adsorption Pretreatment Mass & Heat Pellet Form Transfer

CATALYTIC CHEMISTRY Surface Chemistry and Physics Physical Chemistry Solid State Physics Patents Literature Experimental Programs
PATTERNS OF BEHAVIOR THEORIES OF CATALYSIS

ChE 511 - Catalysis

Prof. Dr. Ik nal

CATALYST DESIGN

New Experimental Commercial

CATALYST TESTING

Exploratory Bench Reactors Model Reactions

CATALYST PREPARATION Laboratory Methods Small Scale Preparation Parameters

COLLOID CHEM. Techniques Description

COMMERCIAL MANUFACTURE Scale-up of Procedures Plant Formulations Large Batches PILOT UNIT TESTING Real Feeds Process Conditions Process Variables Life-time Studies Scale-up Data PROCESS DESIGN Process and Economic Optimization Plant Design

UNIT OPERATIONS Precipitation Washing Drying Calcining Solid Handling

REACTOR ENG. Unit Design and Operation Data Analysis Modeling CHEMICAL AND MECHANICAL ENG. Plant Design Materials Specifications

ChE 511 - Catalysis

Prof. Dr. Ik nal

TARGET REACTION STOICHIOMETRIC ANALYSIS THERMODYNAMIC ANALYSIS

MOLECULAR MECHANISM SURFACE MECHANISM

REACTION PATH CATALYST PROPERTIES CATALYTIC MATERIALS PROPOSED CATALYST Steps in catalyst design

ChE 511 - Catalysis

Prof. Dr. Ik nal

TARGET REACTION CHEMISTRY DATA BASE THERMODYNAMIC DATA BASE REACTION DATA FILE

LIST STOICHIOMETRIC REACTIONS GENERATE THERMODYNAMIC PARAMETERS Operator Input Operator Input PROPOSE MOLECULAR MECHANISMS

PROPOSE SURFACE MECHANISMS

SURFACE CHEMISTRY FILE

Operator Input

DEFINE CATALYST PROPERTIES PROPOSED CATALYST

CATALYST PROPERTY FILE

ChE 511 - Catalysis

Prof. Dr. Ik nal

Propylene Oxide Formation on Cu2O (001) Surface (by utilizing, DFT, VASP code)

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Relative Energy Profile of Propylene Oxide, Propionaldehyde and Allyl Radical Formation
1 0,5 TS (PO) 0 -0,5 -1 -1,5 -2 -2,5 -3 -3,5 -4 -4,5 C3H6 (ads)
Relative Energy (eV)

Allyl-radical(g)

PO (g)

PO(ads) Acetone (g) TS(Acetone) OMMP2(ads) TS(Acrolein) Acetone (ads) Allyl-radical (ads) Acrolein(ads) Acrolein (g)

Surface Intermediate Type Mechanism and Acrolein Formation Pathway on Cu2O(001)

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ChE 511 - Catalysis

Prof. Dr. Ik nal

R1 A R2

B R3 C CH2

Ag CH2=CH2 + O2 Pt PdCl2, CuCl2, HCl Homogeneous

O CH2 2 CO2 + H2O

CH3CHO

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ChE 511 - Catalysis

Prof. Dr. Ik nal

REACTION MECHANISM

KINETICS (MACROSCOPIC LEVEL) DYNAMICS (MICROSCOPIC LEVEL)

HETEROGENEOUS CATALYSIS BY METALS

SYNTHESIS OF CATALYSTS
SOLID STATE CHEMISTRY

CHARACTERIZATION OF CATALYSTS
STRUCTURE, TEXTURE, SPECTROSCOPY, AND DIFFRACTION

SURFACE AND COLLOID CHEMISTRY ORGANOMETALLIC CHEMISTRY

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ChE 511 - Catalysis

Prof. Dr. Ik nal

HOMOGENEOUS CATALYSIS

CHO CH3-CH2 CH3-CH=CH2 + CO + H2 Complex Propylene Liq. Phase Catalyst

Co

CH3 isobutylaldehyde

CH3-CH2-CH2-CHO n-butylaldehyde

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ChE 511 - Catalysis

Prof. Dr. Ik nal

HETEROGENEOUS CATALYSIS
Solid Phase Catalyst Acid Catalyst
(Phosphoric Acid Type or ZSM-5 Type) C2H5 C2H5 Ethylbenzene

+ H2C=CH2
Benzene Ethylene

Dehydrogenation Catalyst

C2H5-CH=CH2
Styrene

Ethylbenzene

[Fe3O4-type]

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Cellulose Acetate C + H2O

(CH2)n Polyethylene (polyethene)

(base for photographic film) CH4 Methane

Substitute Natural Gas

Coal or biomass

+Cellulose

Ru Alkanes, Fe, Alcohols, Co Alkenes (fuels, aviation or diesel), solvents, detergents CH2OH CH2OH And related glycols (antifreeze agents) CO+ H2

Ni/Al2O3

+ CO CH3OH

Acetic Acid

Cu/ZnO

Syn-gas

Methanol
CH3 Zeolite Ag Zeolite (CH2)n Petrol (fuel) Polymers (fabrics and building materials)

HCHO Formaldehyde

CH4 + O2 Natural Gas

Toluene (solvent)

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Ehom Ehet
Potential Energy

Reactants

Products Reaction Coordinate

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ChE 511 - Catalysis

Prof. Dr. Ik nal

6
Log10 (rate constant), arbitrary units

Ahom

Ahet
3

Homogeneous Reaction

Heterogeneous Reaction Measurable Range

1 X 0 1 2 3 Y 4 5 6 7

103/T

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

SURFACE ASSISTED (CATALYTIC) REACTIONS

Example: Catalytic Hydrogenation of Ethylene

C2H4 + H2
G

C2H6

Postulated Mechanisms:
For Homogeneous Reaction: G*

C2H4 + H2

C2H4 . H2

Activated Complex

C2H6

Where G* = Free Energy of Activation For Heterogeneous Reaction:

C2H4 + [S]1

G1 G2

C2H4[S]1 C2H4[S]1 H2 C2H6 + [S]1

H2 + C2H4[S]1 C2H4[S]1 H2

G3

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Published Data from Boudart:

At 600K; CuO-MgO Catalyst

A difficult homogeneous reaction is replaced by a more easily executed heterogeneous surface reaction involving adsorbed C2H4 . (Eley-Rideal Mechanism)
These are simply phenomenological models, not mechanisms. The actual mechanism is quite complex.

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ChE 511 - Catalysis

Prof. Dr. Ik nal

HETEROGENEOUS CATALYSIS MUST ALWAYS BE PRECEDED BY ADSORPTION

desorption C

adsorption

B Surface Reaction

Surface Migration

Two possible ways in which heterogeneous catalysis proceeds at a surface; the Langmuir-Hinshelwood Mechanism (left) and the Eley-Rideal Mechanism (right)

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Methyl Cyclopropane Butene

H
Butane

C-C=C-C

C-C-C-C

Support Metal

A bifunctional catalyst such as platinum on Al2O3 facilitates the isomerization of methylcyclopropane to 2-butene as well as the hydrogenation of 2-butene to butane (after Boudart)

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Physical Adsorption
Weak Forces of Molecular Interaction (Van der Waals) Small Heats of Adsorption (10-40 kj/mol) Occurs only at ~Tb.p. Equilibrium rapidly attained, low E Highly reversible Multilayer coverage possible Nonspecific, almost indistinguishable from condensation In general, not responsible for catalysis; however may help to form chemisorption precursors Important for determination of total surface area and pore size of catalyst support

Chemisorption
Formation and Rupture of Chemical Bonds Large Heats of Adsorption (80-400 kj/mol) No such restriction at high T Nonactivated: Low E Activated: High Often Irreversible Less than a monolayer Highly specific (a function of a particular crystalline face) Necessary for catalysis Important for determination of activecenter surface area and elucidation of surface reaction kinetics

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

Oxidation of CO to CO2 Pd-Ce0.75Zr0.25O2 Catalyst Surface Quantum Mechanical DFT Calculations

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

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ChE 511 - Catalysis

Prof. Dr. Ik nal

DFT COMPUTATIONS
CO conversion energetics
COgp
0,0 1 20,0 40,0 3 5 7 9 11

RelativeEnergy(kcal/mol)

CO2des
60,0 80,0 100,0

O2gp

PdCeZrO2

2nd COgp COads O2ads

120,0 140,0 160,0 180,0 200,0

2nd CO2 2CO2gp

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ChE 511 - Catalysis

Prof. Dr. Ik nal

The Langmuir Treatment of Adsorption Ideal Surface Requirements 1. Energetically homogeneous or uniform surface; 2. Energy of interaction with the adsorbate is not affected by the presence or absence of adsorbate on adjoining sites; 3. Each site can accommodate only one adsorbate molecule or atom; 4. Adsorption would occur when an adsorbate molecule or atom with the required energy strikes an unoccupied site; 5. The energy contours would be unaffected by the extent of adsorption; 6. All adsorption has the same mechanism; each has the same structure; 7. The extent of adsorption is less than one complete monolayer

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ChE 511 - Catalysis

Prof. Dr. Ik nal

If ra=Rate of adsorption, rs= No. of molecules striking the surf./ time-area (bare surf.) Then r a= s . rs ra=kaPA(1- ) where; ka=Ads. Rate Const. =Fraction occupied by already adsorbed molecules Also if rd= Rate of desorption rd=kd At Equilibrium: ra = r d

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ChE 511 - Catalysis

Prof. Dr. Ik nal

ka If A+S kd AS (Elementary Step)

with microscopic reversibility, then

and

Introduce

Where V=Vol. Adsorbed Vm= Vol. Adsorbed by all the active sites covered

NOTE: This treatment is applicable to both physical ads. & chemisorption

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