Hulteberg Chemistry & Engineering

Catalysis – from idea to implementation

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 Company
• We
– specialise in
heterogeneous catalysis
– cover the full chain from
R&D to production
– can assist you anywhere
from idea to
implementation

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 Outline
• Introduction
• General considerations
• Homogeneous catalysis
• Heterogeneous catalysis
– Structure and components
– Development and testing
– Deactivation
– Manufacturing

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 Introduction
• Catalysis involved in a majority of all processes
– Largest catalytic process: photosynthesis
– Omnipresent in the processing of
• Fuels
• Chemicals

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5
 Introduction
• ”to awaken affinities, which are asleep at a
particular temperature, by their mere presence
and not by their own affinity“ – J.J, Berzelius,
1835
• In other terms, a catalyst is a substance that in a
small amount causes a large change
• Does however not cover the industrial case with
slow deactivation:
• “a catalyst is a substance that increases the rate
of reaction toward equilibrium without being
appreciably consumed in the process”
 General considerations
• Important concept: the active site
– The site forms a complex with a reactant and
products are formed
Reactant + Site  Complex  Product + Site
– The original site is restored
 General considerations
• Catalysts come in many shapes and forms
– Protons
– Lewis or Brønstedt acids
– Organometallic complexes
– Organic and inorganic polymers
– Enzymes
– Inorganic materials
 General considerations

Examples of catalysts
 General considerations
• The changes to catalysts are far from
stoichiometric
• Excludes initiators added to polymerisation
– Hydrogen peroxide, ozone
– Is not reformed after reaction
• Excludes action of:
– Heat
– Microwaves
– Photochemical/UV
 General considerations
• The catalyst does not change the ultimate
equilibrium
• The catalyst only accelerate the rate of
approach to equilibrium ”If thermodynamics is the start
and end point in the mountain
range of energy, kinetics is the
road taken between these
points”
 General considerations
• Homogeneous catalysis – the catalyst and the
reactants/products are present in the same phase
– Liquid phase most common
– Catalyst vary, e.g. acids, bases, organometalic
complexes
• Heterogeneous catalysis – the catalyst and the
reactants/products are in different states of
aggregation
– Solid/liquid
– Solid/gaseous
– Catalysts are oxides, metals, supported metals etc.
 General considerations
• The original site must be restored
• Should not be interpreted as that there is not
change to the site
– Metals may be recrystallized
– Oxides may lose oxygen
– Homogeneous catalysts undergo a number of
reactions
 General considerations
• Activity – the rate with which a catalyst cause
a reaction to proceed towards chemical
equilibrium
– Expressed as space-time yield for reactors
• kg s-1m-3
• mol h-1L-1
– Depend on T, P, Cin etc.
 General considerations
• Activity
– may be determined at a standard condition (T, P,
VCatalyst)
– may be reported as a single rate constant (true
kinetics required)
– may be expressed as the temperature for
achieving a certain conversion (T50)
– may be given as the amount of catalyst required
for converting a given inlet feed at a given
operation temperature and pressure
 General considerations
• Selectivity

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑡𝑜 𝐵

𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦𝐵 =
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

• Ethanol can react to release H2 or H2O to

acetaldehyde or ethylene
• Selectivity is determined based on the
resulting products
 General considerations
• Yield similar to selectivity

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐵 𝑓𝑜𝑟𝑚𝑒𝑑

𝑌𝑖𝑒𝑙𝑑 =
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

• More relevant as an industrial measure

 General considerations
• Turn-over number is the number of times a
homogeneous catalyst can convert reactant A to
product B
• In heterogeneous catalysis this relates to the
active site but is defined per g of catalyst for
practical reasons
• The turn-over frequency is the turn-over number
divided by a unit of time
• Make sure to define the unit to avoid confusion
 General considerations
• Space velocity is the inverse of space time
1
– 𝑆𝑝𝑎𝑐𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 =
𝑆𝑝𝑎𝑐𝑒 𝑡𝑖𝑚𝑒
– Defined different for homogenous and heterogeneous
systems
𝑄0𝑁𝑇𝑃
• Homogenous: 𝑆𝑉 = or VHSV for hours
𝑉𝑟𝑒𝑎𝑐𝑡𝑜𝑟
𝑄0 𝑄0𝑁𝑇𝑃
• Heterogeneous: 𝑊𝐻𝑆𝑉 = 𝑜𝑟 𝐺𝐻𝑆𝑉 =
𝑊𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑉𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡

• Gives units as inverse seconds, hours or per m3 of

catalyst
 General considerations
• Typical space velocities (GHSV)
– Steam reforming 1,000 - 3,000 h-1
– Catalytic total oxidation 10,000 - 50,000 h-1
– Ammonia synthesis 5,000 - 10,000 h-1
– HDS of heavy residues 1 h-1 (WHSV)
– SCR depends on position
• High dust 3,000-6,000 h-1
• Low dust 6,000-10,000 h-1
• Tail-end 8,000-12,000 h-1
 General considerations
• Reaction rate for batch reactor (AB)

𝑑𝐴 𝑑[𝐵]
𝑟=− =
𝑑𝑡 𝑑𝑡

𝑟 = 𝑘 ∗ [𝐴]

• k is the reaction rate constant

 General considerations
• For more complex reactions (A + 2B  3C + D)

𝑑𝐴 1𝑑 𝐵 1𝑑 𝐶 𝑑[𝐷]
𝑟=− =− = =
𝑑𝑡 2 𝑑𝑡 3 𝑑𝑡 𝑑𝑡
 General considerations
𝐸
− 𝑎
𝑘 =𝐴∗ 𝑒 𝑅𝑇

• k depends on temperature (strongly) and pressure (weakly)

• k doubles for every 10 C increase
• Activation energy (Ea) key parameter in catalysis
• 8-100 kJ/mol below 20 kJ/mol diffusion limited
• Pre-exponential factor A~ 1011-1014
• No physical explanation for A
 General considerations

𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = ln(𝐴)
Plotting for obtaining A and Ea

𝐸𝑎
𝑆𝑙𝑜𝑝𝑒 = −
𝑅
General considerations

Temperature dependence of the activation

energy
 General considerations

• Rate-limiting step
– Catalytic cycle consist of several (many)
elementary reactions or steps
– The rate of reaction is limited by the slowest
step
– One single step determines the overall
reaction rate, not a sum or average
 General considerations

Reaction steps in a catalytic reaction

 General considerations

• Reaction order
– Usually complex when considering all steps
– Fortunately they can be reduced to 0th , 1st or
2nd order due to the rate-limiting step
𝑑[𝐴]
− = 𝑘 (𝑧𝑒𝑟𝑜 𝑜𝑟𝑑𝑒𝑟 𝐴 → 𝐵)
𝑑𝑡
𝑑[𝐴]
− = 𝑘([𝐴0 ] − [𝐴]) (𝑓𝑖𝑟𝑠𝑡 𝑜𝑟𝑑𝑒𝑟, 𝐴 → 𝐵 + 𝐶)
𝑑𝑡
𝑑[𝐴]
− = 𝑘([𝐴0 ] − [𝐴])([𝐵0 ] − [𝐵]) (𝑠𝑒𝑐𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟, 𝐴 → 𝐵 + 𝐶)
𝑑𝑡
 General considerations

• Adding a catalyst changes the reaction rate

• Also induces change in the rate law
𝑟𝑎𝑡𝑒 = 𝑘[𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡]𝛼 [𝐴]𝛽 [𝐵]𝛾

• Multiple kinetic expressions in catalysis, e.g.

– Langmuir-Hinselwood (heterogenous)
– Elay-Rideal (heterogenous)
– Michaelis-Menten (homogenous)
 General considerations

• Langmuir-Hinshelwood
– Assumes adsorption of gases on a surface
– Reaction occur at active site
– Products desorb
– Diffusion from and into the bulk may be included
• Reactions
– Steam reforming on Ni catalyst
– Ammonia synthesis on Fe catalyst
 General considerations

• Elay-Rideal
– Assumes adsorption of one reactant on
catalyst
– Reaction occur at active site between
adsorbed reactant and molecule in fluid
– Products desorb
• NOx removal good example
 General considerations

• Michaelis-Menten
– Reaction between catalyst and reactant
– Formation of a reversible complex
– Decomposition of complex to catalyst and
product
• Enzymatic reactions, homogeneous
catalysts
 General considerations

• Interaction required with catalyst for reaction

• Not to strong and not to weak
adsorption/reaction/ complexation
• To strong interaction: poisoning
• Sabatiers principle
• Heat of adsorption functional parameter
• Volcano plot
General considerations

Volcano plot
 General considerations
• Summary
– Active site important concept (not empty)
– Active site is recovered (or consumed to a much
lower degree than stoichiometry)
– The catalyst does not change the ultimate
equilibrium
– Heterogeneous/homogeneous catalysis
– Reaction mechanism (LH, MM)
 Homogeneous catalysis
• Covers all types of reactions where the
catalyst and the products/reactants are in the
same state-of-aggregation
• Examples exists of gas/gas (lead chamber) but
is most common as liquid/liquid
• Usually only one type of active site
• Well defined chemical composition
 Homogeneous catalysis
• Homogeneous phase also when reaction with
gases (e.g. H2) dissolved in liquid
• Synonymous to organometallic complexes
• Major issues are
– Catalyst activity
– Catalyst life
– Catalyst separation and recovery
 Homogeneous catalysis
• Catalyst can be
– Acids
– Bases
– Organometallic complexes
– Organic compounds
 Homogeneous catalysis

Examples of homogeneous catalysts

 Homogeneous catalysis
• Catalytic cycle built up by elementary steps
– dissociation and coordination
– oxidative addition
– reductive elimination
– insertion and migration
– de-insertion and ß-elimination
– and nucleophilic attack on coordinated substrate
• Can be used to construct new cycles
 Homogeneous catalysis

Elementary reaction-steps in homogeneous

catalysis
 Homogeneous catalysis

Propene hydroformulation catalytic circle

 Homogeneous catalysis
• Summary
– Catalyst and reactants/product in same phase
– Well defined active site
– Elementary reactions build up cycle
– Organometallic catalysts most common
– Acetic acid, oxo process commercial examples
– Synthesised as fine chemcials
– Recycle and recovery most important in
development
 Heterogeneous catalysis
• Heterogeneous catalysis is the workhorse of the
chemical industry
• 90% of all chemicals by volume involve catalysts
in their production
• 800,000 tonnes produced annually
• $29.5 billion market cap and growing
• Refinery catalysts passed €2 billion in 2005
• Refinery segment growing by about 3% per
annum (environmental)
 Heterogeneous catalysis
• Usually gaseous reactants over catalysts at
high temperature
• Combines multiple areas of research
– Material science
– Surface chemistry
– Thermodynamics and kinetics
– Solid state physics
– Inorganic and organic chemistry
– Engineering
 Heterogeneous catalysis
• Area with much research activity
– Numerous books
– More than 18,000 research papers
• Fortunately all applications rest on a few
fundamental principles
 Heterogeneous catalysis
• Structure
– An industrial catalyst consist of three (3) parts
• Carrier
• Support
• Active phase
– Each with its own purpose
 Heterogeneous catalysis
• Carrier
– Provide structure to the reactor bed
– Determinant of heat and mass transfer
– Determines bed pressure drop (Erguns equation)
– Can be ceramic or metallic
– Should be resistant to mechanical stress
 Heterogeneous catalysis

Different catalyst carriers.

 Heterogeneous catalysis
• Support
– Provide surface area for reaction
– May be the material of the carrier
– Common materials
• Alumina
• Silica
• Ceria
• Mixed oxides
• Active carbon
 Heterogeneous catalysis
• Support
– Surface area important feature
– Measured as m2/g
– Porosity
• Micropores (< 2 nm)
• Mesopores (2-50 nm)
• Macropores (> 50 nm)
 Heterogeneous catalysis
• Support
2
Material Area (m /g)
γ-alumina 180
Activated charcoal <1,100
Silica-alumina 250
Silica gel 200
Zeolite 900

A football pitch has a surface of 7,140 m2

Equals ~40 g of γ-alumina
 Heterogeneous catalysis
• Active phase
– Contain sites where reaction occur
– Metals or metal oxides
– Metals from transition metal group in periodic table
• Pt
• Pd
• Cu
• Co
• Ni
• Rh
Heterogeneous catalysis

Most active
phases
Most catalyst
poisons
 Heterogeneous catalysis

The different elements to heterogeneous catalysis

 Heterogeneous catalysis
• Surfaces not as perfect as believed
– Kinks
– Steps
– Crystal imperfections
– Vacancies
• Imperfections often active site
 Heterogeneous catalysis

Examples of active sites

 Heterogeneous catalysis
• Active sites most often not preferred
adsorption site
• Follow the Sabatier principle
– Good enough for adsorption
– Still allow for desorption of product
• Ideally all sites are alike and not in contact
with each other
• Not the case in industrial catalysts
 Heterogeneous catalysis
• Support and active phase not always
separated
• Strong metal support interactions (SMSI)
– Spill over effects between the support and the
active phase
– Three-way catalyst good example
– Rh/CeO2
– Ceria involved in oxygen transfer
 Heterogeneous catalysis
• Promoters and modifiers
– Added to active phase, support or carrier
– To promote activity (or decrease it)
– To block side-reactions
– Prolong catalyst life
– Improve textural properties
• Based on empirical observation
• Long-term effects
• Often left out of academic research
 Heterogeneous catalysis
• Catalysis syntax
– Often uncertain which phase is active
• Metallic
• Oxide
• Sulphide etc.
– CoMo/Al2O3 denotes Co and Mo (active phase)
supported on aluminium oxide (support)
 Heterogeneous catalysis
• Characterisation
– Surface area methods
– Temperature programmed methods
– Spectroscopy/microscopy methods
 Heterogeneous catalysis
• Surface area methods
– Key is accessibility of reactants to the surface
– Use adsorption with different probe moleculesor
physical phenomenon
• BET
• Mercury intrusion porisomitry
• Chemisorption
– Differentiate physisorption from chemisorption
• Physisorption (10-40 kJ/mol)
• Chemisorption (80-400 kJ/mol)
 Heterogeneous catalysis
• Temperature programmed methods
– Methods in which temperature is changed to
show influence of environment
• Reduction
• Oxidation
• Desorption
• Reaction
– Give fingerprints suitable for comparison within a
series of measurements
– Can be used for calculating heats of ads. etc.
 Heterogeneous catalysis
• Spectroscopic methods
– Bulk or surface sensitive depending on radiation
type
• X-ray diffraction
• Raman spectroscopy
• Electron microscopy
• XPS
– Either ex-situ or in-situ studies
 Heterogeneous catalysis
• Catalyst testing important for several reasons
– Catalyst discovery
• Activity
• Selectivity
• Kinetics
• Mechanisms
– Catalyst diagnostics
– Catalyst life

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 Heterogeneous catalysis
• Reactor purpose
– Catalyst discovery (scouting reactor)
– Catalyst improvement/industrialisation (catalyst-
optimization reactor)
– Pilot testing (prototype reactor)
 Heterogeneous catalysis
• Scouting reactor
– Measure activity
– Minimal influence of gradients
• Temperature
• Diffusion
– Easy to exchange catalyst
 Heterogeneous catalysis
• Scouting reactor
– Try to measure parameters that are not influenced
by heat and mass transfer
– Intrinsic kinetics
– If not possible, estimate influence of heat and
mass transfer
– Use numerical models that include diffusion for
evaluation
 Heterogeneous catalysis
• Gradients may be
– Intraparticular
– Interparticular
• In the film on the outside of the catalyst particle
• Inside/outside gas-bubbles in gas/liquid/solid systems
– Reactor gradients
• Radial
• Axial
 Heterogeneous catalysis
• Criteria for testing first suggested by D.E. Mears
– D.E. Mears, Ind. Eng. Chem. Process. Develop., 10(4),
1971, 541-547
– Complemented by S.T. Sie, (AIChE Journal, 42(12),
1996, 3498-3507) for gas phase and trickle flow beds
• If criteria are met the observed reaction rate is
within 5% of the intrinsic reaction rate (”the
reaction rate without influence of outer or inner
mass or heat transfer”)
Heterogeneous catalysis

The effectiveness factor and its relation to the Damköhler number

 Heterogeneous catalysis
• Activation energy may also be used to assess if
there are gradients

Kinetic region: Ea
Intraparticle diffusion: Ea/2
Interphase mass transfer: about 8 kJ/mol
 Heterogeneous catalysis
• Catalyst-optimization reactor
– Bringing successful candidates towards
commercialization
– Prepare and test catalyst in satisfactory
commercial form
– Pellets, extrudates or monoliths
– Investigate performance closer to industrial
conditions
– Including gradients
 Heterogeneous catalysis
• Prototype reactor
– Large enough section of a commercial type
reactor
– Used for scale-up
– To determine actual reactor gradients and
performance
• Pressure drop investigated
• Repeatability of reactor packing
• Heat transfer limitations
– Single tube in multi-tube reactor
 Heterogeneous catalysis
• Reactors above can be of different types
– Non-Stationary
• Batch
• Fed batch
• Transient
– Stationary/continuous
• Plug flow
• Fluidized bed
• Continuously stirred tank reactor
 Heterogeneous catalysis
Laboratory reactors

Non-stationary Stationary

Fludized
Batch Fed-batch Transient Plug flow CSTR
bed

Differential Integral

Single pass Recirculating

Internal External
 Heterogeneous catalysis
• Catalyst manufacturing
• Involves many different steps
– Support preparation
– Active phase preparation
– Post-treatment
– Forming
– Activation
 Heterogeneous catalysis
• Two main classes of catalysts
• Bulk catalysts
– Ammonia synthesis
– Hydrocracking
– Zeolites
• Impregnated catalysts
– Precious metal based
 Heterogeneous catalysis
Bulk Impregnated
Impregnated
catalysts catalysts
catalysts

Precipitation Wet
(Silica/ impregnation
Alumina) (Automotive)

Hydrothermal Incipient
synthesis wetness
(Zeolites) (Pt/Sn/Al2O3)

Fusion/alloy
Ion exchange
leaching
(Acidic zeolite)
(Mixed oxides)
 Precipitation
Support preparation
Gelation

Impregnation
Active phase
preparation
Ion exchange
Filtration

Drying Post-treatment

Calcination
Extrusion
Forming
Pelleting

Activation

Unit operations of catalyst manufacturing

 Heterogeneous catalysis
• Deactivation may have several causes
• Such as:
– Over-temperature
– Changes in inlet composition
– Process hygiene
• Concerns the deactivation that occur after the
first initial lowering of activity
• After 50 -100 h and onwards
Heterogeneous catalysis
 Heterogeneous catalysis
• Poisoning
– Interaction with the active phase
– Usually with an electronegative specie
• Sulphur
• Chlorine
• Arsenic
• Phosphorous
• But also other compounds (e.g. CO, O2, NH3)
Heterogeneous catalysis

Most active
phases
Most catalyst
poisons
 Heterogeneous catalysis
• Fouling
– Covering of the active part of a catalyst
– Physical blocking of active sites
– Physical blocking of pores
– Renders part of the catalyst useless
– Can be formed or introduced
• Coke formation
• Ash coverage
 Heterogeneous catalysis
• Sintering
– Two types
• Active phase
• Support
– Results in loss of metal surface directly or
indirectly
 Conclusions
• Catalysts omnipresent in the industry
• Accelerates reactions and favors chosen
products
• Two types
– Heterogeneous
– Homogeneous

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