Hulteberg Chemistry & Engineering

Catalysis – from idea to implementation

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Copyright © 2016 by Christian Hulteberg

All rights reserved. This handout or any portion thereof may not be reproduced or used in any manner
whatsoever without the express written permission of the publisher except for the use of brief quotations.

Hulteberg Chemistry & Engineeing AB

Rödklintsgatan 2b
218 73 Tygelsjö
Sweden

www.Hulteberg.com

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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
• Catalyst manufacturing
– Bulk catalyst
– Impregnation of pre-shaped bodies
• Conclusions

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 Introduction
• Area with very little publications
• Two main classes of catalysts
• Bulk catalysts
– Ammonia synthesis
– Hydrocracking
– Zeolites
• Impregnated catalysts
– Precious metal based
– VOC-abatement catalysts (base metal)
 Introduction
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)
 Bulk catalysts
• Starting from metal salts
• Prepared such that the entire catalyst is made
from the active material
• Multi-step process
 Bulk catalysts
Precipitation
Catalyst preparation
Gelation
Filtration

Drying Post-treatment

Calcination Extrusion

Forming Tableting

Granulation

Activation

Unit operations of bulk catalyst manufacturing

 Bulk catalysts
• Precipitation/gelation
– Mixing of metal salts in stirred container
– Changing (increasing) pH lowers solubility of salts
– The salts precipitate/fall out of solution or form a gel
• Equipment
– Stirred tanks with heating/cooling
– Normal operating temperature is ambient to 60°C
– Stainless steel most common (beware of corrosion
products)
– Cleaning is an issue in multi-product tanks

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 Bulk catalysts
• Precipitation may need aging (secondary
precipitation) in tank
• Needs moving from tank in slurry form
– Pumping
– Gravity
• In pumping avoid structural changes due to
shearing
 Bulk catalysts
• Filtration
– Normally quite difficult
– Maximising surface area of catalyst implies
gelation in most cases
– Gel-like precipitates are notoriously difficult and
slow to filter
– Temperature and pH of slurry key performance
parameters
 Bulk catalysts
• Filtration
– Using ordinary filtering techniques
– Plate and frame filters
– Rotary vacuum filter
– Line filters
– Disk filters
• Centrifugation also possible
 Bulk catalysts
• Drying
– Takes the wet filter cake and dries it
– Heat for drying
• Electric
• Combustion of fuel
– Ensure combustion product does not touch catalyst
(heat exchanger)
– CO and other components may act detrimental on
catalyst
– In recirculating drying ovens, catalyst particle transfer
may be a problem
 Bulk catalysts
• Drying
– Tunnel dryer
– Drum dryer
– Flash dryer
– Spray dryer
 Bulk catalysts
Feed
Air • Fluidized catalyst
• Small particle catalysts
• Good for gel handling

Exhaust
Air

Product

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 Bulk catalysts
• Calcining
– Heat treatment of catalyst
– Final temperature depend on material and
application
– Normal operating temperatures from 500 to
1,000°C
– Transformation of state
• e.g. from nitrate to oxide
• Or from bohemite to γ-alumina
 Bulk catalysts
• Calcining
– Large influence of atmosphere
– Gas (air) flow through catalyst common
– Recirculation of air may improve performance
– E.g. high concentrations of NOx in furnace may
slow down decomposition process and yield
smaller particles (for supported metal catalysts)
 Bulk catalysts
• Calcining
– Batch
– Continuous
• Belt furnace
• Rotary kiln
 Bulk catalysts
• On precipitation foreign ions are trapped
– Sodium / other alkali
– Anionic compound (Cl-, SO42-)
• Will be to firmly boxed in e.g. on gelling to
wash out from precipitate
• Therefore rewashing after calcination removes
these ions
• Ammonium carbonate may also be used to ion
exchange for even higher purity
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Bulk catalysts
• Forming
– Required for non-
fluidized catalysts
– Pre-densification
required
(kneading)
– Can be
accomplished in
washing/ion
exchange
– Combined with
addition of
tableting aids or
binders 20
 Bulk catalysts
• Forming
– Tableting
– Extrusion
– Granulation (spherudizing)
• Inevitable lower activity compared to powder
• Introduces
– Diffusion limitations
– Aids for forming (graphite, silicates, MgOH/MgO)

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 Bulk catalysts
• For tableting the densified powder is dried
and pulverized
• Powder is screened
– 6 mesh if 12-18 mm (1/2” to 3/4”)
– 10 or 12 mesh if 6-10 mm (1/4” to 3/8”)
• Pilling aid may also be introduced at this stage
• May require post-calcination

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Bulk catalysts

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 Bulk catalysts
• Extrusion combined with densification
• Moist clay of catalyst powder + water + binder
• Pushed through a die to form catalyst
– Round
– Trilobe
– Quatrolobe
– Other shapes
• Limits in size 20 mm in diameter
• Expansion after die
• Dried, calcined, post-treated

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Bulk catalysts

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Bulk catalysts

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 Bulk catalysts
• Granulation
– Spraying slurry on tilted disk/pan
– Disk rotates and spheres build up
– Large particles are concentrated to top layer
– Falls out of pan at different size depending on tilt
angle
– Less uniform than tabletting
– Requires post treatment

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Bulk catalysts
 Pre-shaped bodies

Different catalyst carriers.

 Precipitation
Support preparation
Gelation
Filtration

Drying Post-treatment

Calcination Extrusion

Forming Tableting

Granulation
Impregnation Active phase
preparation
Ion exchange

Drying
Post-treatment
Calcination

Unit operations of catalyst manufacturing

for pre-shaped bodies
Activation
 Pre-shaped bodies
• Two types of treatments
– Washcoating of monoliths
– Impregnation of active phase on support
• Incipient wetness
• Wet impregnation
• Washcoating
– Wet milling powder of support
– Mixed with additives for rheology and
– Binding agent

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 Pre-shaped bodies
• Washcoating performed on multiple carriers
– Metal monoliths
– Cordierite monoliths
– Ceramic and metallic foams
• Slurry applied by dip-coating or pump-through
• Excess slurry removed by pressurized air

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 Pre-shaped bodies
• Incipient wetness
– Measure catalyst pore volume
– Prepare solution of chemical salt with correct
concentration
– Add controlled amount such that the catalyst is
still dry to the touch
– Dry and calcine (preferably in same container)
• Will yield rather even distribution of material
in body

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 Pre-shaped bodies
• Wet impregnation
– Large excess of active phase solution
– Normally very low concentrations
– Adsorption (chemical interaction) between ions in
the solution and the material of the body
– Remove from liquid, dry and calcine
• Will yield varying distributions as a function of
pH (iso-electric point)

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 Pre-shaped bodies

Homogenous Egg-shell Ring Egg-yolk

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 Conclusions
• To large extent experience-based activity
• Many steps involved in forming a catalyst
– Chemical
– Thermal
– Mechanical
• Recipes trade secrets and include everything
from main chemicals to structural promotors
and processing steps

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 Further reading
• Catalyst Manufacture, Alvin B. Stiles, Theodore A.
Koch, vol. 63 of Chemical Industries, CRC press
1995
• Handbook of Heterogeneous Catalysis, vol 2,
Gerhard Ertl, Helmut Knözinger, Ferdi
Schüth, Jens Weitkamp, Wiley, 2008
• Catalysis: An Integrated Approach to
Homogeneous, Heterogeneous and Industrial
Catalysis, J.A. Moulijn, P.W.N.M. van Leeuwen,
R.A. van Santen, Elsevier, 1993
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 Thank you

Christian@Hulteberg.com
+46733969420

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