Part 1: The Nature of Catalysts

Reactors and catalysis: heterogeneous catalysis

importance of catalysis how catalysts work adsorption quantifying adsorption BET and Langmuir isotherms heterogeneous reaction kinetics use of Langmuir isotherms unimolecular and bimolecular reactions adsorption and reaction controlled reversible reactions
With thanks to Robert Fishwick for use of the notes

Part 1: The Nature of Catalysts

syllabus
heterogeneous catalysis

the nature of catalysts (with examples) and how they work

adsorption (chemisorption, physisorption) surface area and the BET equation the Langmuir isotherm kinetic modelling of unimolecular and bimolecular reactions for systems controlled by adsorption, surface reaction or desorption
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Part 1: The Nature of Catalysts

learning outcomes
By the end of the module the student should be able to understand and describe the fundamentals of catalysis and catalytic reactors

additional reading

Reactor Design for Chemical Engineers, J.M. Winterbottom and M.B. King Chemical Reaction Engineering, O. Levenspiel 3

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Part 1: The Nature of Catalysts

a brief history of catalysis

Catalysis coined by Jns Berzelius in 1836

first real industrial catalysis in 1875: large-scale production of sulphuric acid on platinum, invented by Peregrine Philips

Ostwald develops ammonia oxidation on Pt gauze to produce nitric acid in 1903

Bosch and Haber develop the ammonia synthesis process around 1908 to 1914 to allow manufacture of fertilizers

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Part 1: The Nature of Catalysts

a brief history of catalysis

1897: Paul Sabatier discovers the use of finely divided nickel to hydrogenate hydrocarbon double bonds 1905: Wilhelm Normann started large scale production of hydrogenated oils in Warrington on nickel catalyst, currently 4MMtpa of hardened fats are produced worldwide

1920s: further developments in hydrogenation catalysts provide new routes to fine chemicals and pharmaceuticals 5

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Part 1: The Nature of Catalysts

a brief history of catalysis

1930: conversion of H2 and CO to CH4 and higher hydrocarbons on Fe and Ru in the Fischer-Tropsch process, used to produce fuel in wartime Germany 1937: partial oxidation of ethene to ethylene oxide on Ag/Al2O3 catalyst

1938-1946: development of the Oxo process for the production of aldehydes from alkenes, H2 and CO
1955: stereospecific polymerisation for the synthesis of polyethylene on Ziegler-Natta complexes of titanium 1960: production of acetaldehyde by the oxidation of ethene in the Wacker process using PdCl2-.Cu2+ catalyst
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Part 1: The Nature of Catalysts

a brief history of catalysis

Late 1930s: catalytic cracking developed for the production of branched hydrocarbons from longer chains on aluminosilicate catalysts
1942: Friedel-Craft alkylation for the production C7, C8 hydrocarbons from C3, C4 using acids, AlCl3 1950: catalytic naphtha reforming using Pt/Al2O3 1960s: zeolitic catalytic cracking developed 1960s: hydrodesulphurisation for the removal of sulphur from diesel fuel developed on CoMo/Al2O3 catalyst
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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

a brief history of catalysis

1970s: development of three-way catalytic converter for car emission-control using Pt/Pd/Rh catalyst
aHC + bO2 cCO2 + dH2O 2CO + O2 2CO2

2NO + 2CO N2 + 2CO2

monolith enclosure

steel housing

monolith
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ceramic monolith lambda probe

measure oxygen content in the exhaust gas
support for catalytic metals

Part 1: The Nature of Catalysts

and in the future?

development trends
milder reaction conditions improved activity and selectivity innovations in contacting and reactor design

emerging catalytic technology energy, fuels and chemicals from natural gas, coal and biomass environmental engineering enzymatic and homogeneous catalysis, immobilization of homogeneous catalysts to aid separation

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

what is a catalyst?

a catalyst is a substance which increases the rate at which a chemical reaction approaches equilibrium, without itself becoming permanently changed by the reaction or altering the equilibrium conditions i.e. catalysts affect equally the forward and reverse reaction rates

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zirconium on alumina

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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Facts and Figures about Catalysts
Life cycle on the earth
Catalysts (enzyme) participates most part of life cycle e.g. forming, growing, decaying Catalysis contributes great part in the processes of converting sun energy to various other forms of energies e.g. photosynthesis by plant CO2 + H2O=HC + O2 Catalysis plays a key role in maintaining our environment

Chemical Industry
90% of chemical industry has catalysis-related processes Catalysts contributes 2% of total investment in a chemical process

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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

What is Catalysis
Catalysis
Catalysis is an action by catalyst which takes part in a chemical reaction process and can alter the rate of reactions, and yet itself will return to its original form without being consumed or destroyed at the end of the reactions (This is one of many definitions) Three key aspects of catalyst action taking part in the reaction
it will change itself during the process by interacting with other reactant/product molecules

altering the rates of reactions

in most cases the rates of reactions are increased by the action of catalysts; however, in some situations the rates of undesired reactions are selectively suppressed

Returning to its original form

After reaction cycles a catalyst with exactly the same nature is reborn In practice a catalyst has its lifespan - it deactivates gradually during use
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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Action of Catalysts
Catalysis action - Reaction kinetics and mechanism
Catalyst action leads to the rate of a reaction to change.
This is realised by changing the course of reaction (compared to non-catalytic reaction)

Forming complex with reactants/products, controlling the rate of elementary steps in the process. This is evidenced by the facts that
The reaction activation energy is altered energy The intermediates formed are different from
uncatalytic
catalytic

those formed in non-catalytic reaction

The rates of reactions are altered (both desired and undesired ones)

reactant produc t reaction process

Reactions proceed under less demanding conditions

Allow reactions occur under a milder conditions, e.g. at lower temperatures for those heat sensitive materials
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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

It is important to remember that the use of catalyst DOES NOT vary DG & Keq values of the reaction concerned, it merely change the PACE of the process
Whether a reaction can proceed or not and to what extent a reaction can proceed is solely determined by the reaction thermodynamics, which is governed by the values of DG & Keq, NOT by the presence of catalysts. In another word, the reaction thermodynamics provide the driving force for a rxn; the presence of catalysts changes the way how driving force acts on that process. e.g CH4(g) + CO2(g) 2CO(g) + 2H2(g)

Action of Catalysts

DG373=151 kJ/mol (100 C) DG973 =-16 kJ/mol (700 C)

At 100C, DG373=151 kJ/mol > 0. There is no thermodynamic driving force, the reaction wont proceed with or without a catalyst At 700C, DG373= -16 kJ/mol < 0. The thermodynamic driving force is there. However, simply putting CH4 and CO2 together in a reactor does not mean they will react. Without a proper catalyst heating the mixture in reactor results no conversion of CH4 and CO2 at all. When Pt/ZrO2 or Ni/Al2O3 is present in the reactor at the same temperature, equilibrium conversion can be achieved (<100%).

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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

The types of catalysts

gas liquid solid

Types of Catalysts & Catalytic Reactions

Classification based on the its physical state, a catalyst can be

Classification based on the substances from which a catalyst is made

Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)
Organic (organic acids, enzymes etc.)

Classification based on the ways catalysts work

Homogeneous - both catalyst and all reactants/products are in the same phase (gas or liq) Heterogeneous - reaction system involves multi-phase (catalysts + reactants/products)

Classification based on the catalysts action

Acid-base catalysts Enzymatic Photocatalysis

Electrocatalysis, etc.
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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Industrial applications

Applications of Catalysis

Almost all chemical industries have one or more steps employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals

Advantages of catalytic processes

Achieving better process economics and productivity
Increase reaction rates - fast Simplify the reaction steps - low investment cost Carry out reaction under mild conditions (e.g. low T, P) - low energy consumption

Reducing wastes
Improving selectivity toward desired products - less raw materials required, less unwanted wastes Replacing harmful/toxic materials with readily available ones

Producing certain products that may not be possible without catalysts Having better control of process (safety, flexible etc.) Encouraging application and advancement of new technologies and materials And many more
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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Applications of Catalysis

Environmental applications
Pollution controls in combination with industrial processes
Pre-treatment - reduce the amount waste/change the composition of emissions Post-treatments - once formed, reduce and convert emissions Using alternative materials

Pollution reduction
gas - converting harmful gases to non-harmful ones

liquid - de-pollution, de-odder, de-colour etc

solid - landfill, factory wastes

And many more

Other applications
Catalysis and catalysts play one of the key roles in new technology development.
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CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Research in Catalysis
Research in catalysis involve a multi-discipline approach
Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation of results obtained under various conditions, generalising reaction types & schemes, predict catalyst performance

Catalyst development
Material synthesis, structure properties, catalyst stability, compatibility

Analysis techniques
Detection limits in terms of dimension of time & size and under extreme conditions (T, P) and accuracy of measurements, microscopic techniques, sample preparation techniques

Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry

Reactor modelling
Mathematical interpretation and representation, the numerical method, micro-kinetics, structure and efficiency of heat and mass transfer in relation to reactor design

Catalytic process
Heat and mass transfers, energy balance and efficiency of process

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CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Catalytic Reaction Processes

Understanding catalytic reaction processes

A catalytic reaction can be operated in a batch manner Reactants and catalysts are loaded together in reactor and catalytic reactions (homo- or heterogeneous) take place in pre-determined temperature and pressure for a desired time / desired conversion Type of reactor is usually simple, basic requirements Withstand required temperature & pressure Some stirring to encourage mass and heat transfers Provide sufficient heating or cooling Catalytic reactions are commonly operated in a continuous manner Reactants, which are usually in gas or liquid phase, are fed to reactor in steady rate (e.g. mol/h, kg/h, m3/h) Usually a target conversion is set for the reaction, based on this target required quantities of catalyst is added required heating or cooling is provided required reactor dimension and characteristics are designed accordingly.
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CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Catalytic Reaction Processes

Catalytic reactions in a continuous operation (contd) Reactants in continuous operation are mostly in gas phase or liquid phase easy transportation The heat & mass transfer rates in gas phase is much faster than those in liquid Catalysts are pre-loaded, when using a solid catalyst, or fed together with reactants when catalyst & reactants are in the same phase and pre-mixed

It is common to use solid catalyst because of its easiness to separate catalyst from unreacted reactants and products
Note: In a chemical process separation usually accounts for ~80% of cost. That is why engineers always try to put a liquid catalyst on to a solid carrier. With pre-loaded solid catalyst, there is no need to transport catalyst which is then more economic and less attrition of solid catalyst (Catalysts do not change before and after a reaction and can be used for number cycles, months or years), In some cases catalysts has to be transported because of need of regeneration In most cases, catalytic reactions are carried out with catalyst in a fixed-bed reactor (fluidised-bed in case of regeneration being needed), with the reactant being gases or liquids

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CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Catalytic Reaction Processes

General requirements for a good catalyst

Activity - being able to promote the rate of desired reactions

Selective - being to promote only the rate of desired reaction and also retard the undesired reactions
Note: The selectivity is sometime considered to be more important than the activity and sometime it is more difficult to achieve

(e.g. selective oxidation of NO to NO2 in the presence of SO2) Stability a good catalyst should resist to deactivation, caused by the presence of impurities in feed (e.g. lead in petrol poison TWC. thermal deterioration, volatility and hydrolysis of active components attrition due to mechanical movement or pressure shock A solid catalyst should have reasonably large surface area needed for reaction (active sites). This is usually achieved by making the solid into a porous structure.

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

catalyst selectivity
a second property of a catalyst is its ability to selectively catalyse a reaction producing a desired product among a number of other reactions
C2H4O + H2

Cu C2H5OH Al2O3

C2H4 + H2O

both reactions favoured thermodynamically

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

how does it increase reaction rate?

provides a lower energy reaction path
E (A*) homo E homo A* hetero E hetero A B activation energy

}DH

enthalpy of reaction
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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

example of potential energy change

Given the reaction:
S(s) + O2(g) SO2(g) + energy Which diagram best represents the potential energy changes for this reaction?
Potential Energy

Potential Energy

Potential Energy

Potential Energy

activation energy enthalpy of reaction

Reaction Coordinate Reaction Coordinate

Reaction Coordinate

Reaction Coordinate

B C

C
Reaction Coordinate

Potential Energy

D
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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

elements with catalytic applications

H Li Be B Al Sc Y Ti V C Si N P O S F Cl Br I He Ne Ar Kr Xe

Na Mg K Rb Ca Sr

Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Ru Rh Pd Ag Cd Ir Pt Au Hg In Tl Sn Sb Pb Bi Te Po

Zr Nb Mo Tc Hf Ta

Cs Ba La Fr Ra Ac

W Re Os

At Rn

Lanthanides

Ce

Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Actinides

Th Pa

Np Pu Am Cm Bk

Cf

Es Fm Md No Lr

catalytic elements poisons

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supports promoters

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CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Solid Catalysts
Catalyst composition
Active phase
Where the reaction occurs (mostly metal/metal oxide)
Catalyst Support

Promoter
Textual promoter (e.g. Al - Fe for NH3 production) Electric or Structural modifier Poison resistant promoters

Support / carrier
Increase mechanical strength Increase surface area (98% surface area is supplied within the porous structure) may or may not be catalytically active
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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

active components
metals hydrogenation, dehydrogenation, hydrogenolysis, oxidation Fe, Ni, Co, Pt, Pd, Rh, Ru, Ir, Cu, Au metal oxides (semi-conductors)

oxidation, reduction, dehydrogenation, cyclization NiO, ZnO, CuO, Cr2O3

metal oxides (insulators)

dehydration, isomerisation Al2O3, SiO2, MgO

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TEM of Pd/Al2O3 catalyst

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

active components

metal sulphides (from oxide precursor) hydrodesulphurisation copper molybdate, Ni3S2 acids polymerisation, isomerisation, cracking, alkylation H3PO4, H2SO4, Al2O3-SiO2 (zeolites), clays homogeneous catalysts

hydrogenation, carbonylation, oxo reactions various metal complexes e.g. Rh(PPh3)Cl can be heterogenised or used in biphasic solvents for separation from products 29

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

unsupported metals
not common as a large metal surface area is desirable examples include wires, gauzes and powders one notable example are skeletal (Raney) species, for example, Raney Nickel produced by leaching the aluminium from AlNi alloys with sodium hydroxide

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

supported metals
the aim is to improve dispersion of the metal species and thereby increase the activity of the catalyst this may be in order to best utilise expensive metals such as platinum and palladium or to stabilise metals such as nickel the most common supports are Al2O3, SiO2, zeolites and activated carbons

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

precipitated catalysts
formed from a liquid solution of the metal and support components, for example:
2Ni(NO3)2 + 2NaOH + Na2CO3 Ni2(OH)2CO3 + 4NaNO3

the key is to control the crystallite size during precipitation and ensure adequate mixing the support may be added a finely divided powder or prepared in the same solution from soluble salts e.g. aluminium salts converted to alumina

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

impregnated catalysts
more commonly used is the impregnation of the porous support with a solution of the active component the support is either dipped in the solution or the solution sprayed onto the support this is followed by drying to remove water and then calcination in air to form insoluble oxides on the support surface this may then be followed by reduction to form crystallites of the metal
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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

egg-shell catalysts
in the case of precious metal catalysts it is desirable to deposit only a low weight percentage on the support in order to minimise diffusional effects through the porous support the metal is often only deposited near the outside of the support to form a so-called egg-shell catalyst this is done by dipping in a strongly adsorbing for a short time followed by immediate drying the dispersion of the metal in the support can be controlled in other ways:
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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

influence of catalyst distribution

e.g. chloroplatinic acid active component catalyst support added as solution

fully disperse

egg-shell low internal diffusion

active component driven into catalyst

e.g. with citric acid RPF

egg-white

egg-yolk good selectivity

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

calcination
calcination is a heat treatment carried out in air at a temperature slightly above the projected operating temperature of the catalyst the aim is to stabilize physical, chemical and catalytic properties thermally unstable compounds are decomposed during the process (e.g. carbonates and nitrates) the crystalline and pore structures are modified

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

reduction
metal oxides may be decomposed to form crystallites of the metal on the support this is usually done by reacting the catalyst with hydrogen at elevated temperatures

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

catalyst pellets
pelleting: the powder is compressed to produce pellets of precise dimensions extrusion: the powder is made into a paste and pushed through a small hole called a die granulation: agglomeration of powder to form small spheres

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1.0 0.9 0.9 0.8 relative pressure drop for various pellets

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

the catalyst surface

Fischer-Tropsch catalyst

Ni-Au surface

planar corner edge terrace adatom edge adatom

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

the catalyst surface

platinum catalyst for the oxidation of carbon monoxide

CO

CO O2 step

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Department of Physical Chemistry, Fritz-Haber-Institut, Berlin

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CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Part 1: The Nature of Catalysts

Example Heterogeneous Catalytic Reaction Process

The long journey for reactant molecules to
j. travel within gas phase k. cross gas-liquid phase boundary l. travel within liquid phase/stagnant layer m. cross liquid-solid phase boundary n. reach outer surface of solid o. diffuse within pore p. arrive at reaction site q. be adsorbed on the site and activated r. react with other reactant molecules, either being adsorbed on the same/neighbour sites or approaching from surface above
gas phase reactant molecule

gas phase

k l

mn
o

liquid phase / stagnant layer

porous solid

pore

Product molecules must follow the same track in the reverse direction to return to gas phase Heat transfer follows similar track

pq r

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

steps in a heterogeneous reaction

gas bubble (A) catalyst particle CAb reaction 4 site
5

CAg

12

pore

bulk liquid (B)

A(g) + B(l) R(l)

CAg CA CAi CAb CAs

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Part 1: The Nature of Catalysts Part 1: The Nature of Catalysts

steps in a heterogeneous reaction

1. 2.

3.

4.

5. 6.

7.
8. 9.

adsorption of A from the gas phase into the liquid interface diffusion of A into the bulk liquid phase from the liquid side of the gas/liquid interface diffusional transport of reactant A from the bulk phase to the external catalyst surface. Applies to B as well, but in this case bulk and surface concentration may be equal except if there is also a solvent present pore diffusion of reactant by molecular and Knudsen diffusion to the internal active surface site adsorption of reactant at active site chemical reaction at active site desorption of product(s) from active site pore diffusion of product(s) to the exterior surface diffusional transport of product(s) to the bulk phase across the surface boundary layer
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Part 2: Adsorption Part 2: Adsorption

physical vs. chemical adsorption

parameter heat of adsorption physisorption low (<20 kJ/mol) none >1 low (< room temperature) chemisorption high (40-650 kJ/mol

energy of activation for adsorption number of layers formed

temperature at which effects are significant
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none in some case but can be 40 kJ/mol or more one only

sub-ambient to temperatures of 800 K and above
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Part 2: Adsorption Part 2: Adsorption

adsorption: adsorption hydrogen on nickel

(a) (b) (c) (d)

Ni

H2

Ni

Ni

Ni

Ni

Ni

Ni

Ni

2.5

1.5

idealised representation of stages in transition from molecular hydrogen to chemisorbed atomic hydrogen (a) approaching surface (b) physisorbed state (c) at transition stage (d) in chemisorbed state 46

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Part 2: Adsorption Part 2: Adsorption

adsorption: hydrogen on nickel

potential energy chemisorption curve

potential energy curves for the chemical and physical adsorption of hydrogen on nickel, and a diagrammatical representation of the adsorbed states

0 -DHC

physisorption EA curve -DHP distance from surface

Ni

In this case activation energy, EA, is positive so there is an energy barrier to chemisorption which will have a major influence on kinetics

Ni

H H

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Part 2: Adsorption Part 2: Adsorption

adsorption : CO oxidation
CO
O2 CO2

+
catalyst adsorption
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reaction

desorption
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Part 2: Adsorption Part 2: Adsorption

quantitative aspects of adsorption

a number of isotherms can be used to describe adsorption
the Brunauer, Emmett and Teller (BET) isotherm the Langmuir isotherm the Gibbs isotherm the Henry isotherm, etc.

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