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 testing
– Reactor types and applications
– Gradients and implications
• Conclusions
• Further reading
• Nomenclature

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 Introduction
• Heterogeneous catalysis is the workhorse of the
chemical industry
• 90% of all chemicals by volume involve catalysts
in their production
• 2,000,000 to 6,000,000 tonnes produced annually
• $29.5 billion market cap and growing
– Omnipresent in the processing of
• Fuels
• Chemicals
• Catalyst research ongoing activity with testing for
activity and selectivity being a central part
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 Introduction
• Catalyst testing important for several reasons
– Catalyst discovery
• Activity
• Selectivity
• Kinetics
• Mechanisms
– Catalyst diagnostics
– Catalyst life

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 Catalyst testing
• Reactor purpose
– Catalyst discovery (scouting reactor)
– Catalyst improvement/industrialisation (catalyst-
optimization reactor)
– Pilot testing (prototype reactor)

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 Catalyst testing
• Scouting reactor
– Measure activity
– Minimal influence of gradients
• Temperature
• Diffusion
– Easy to exchange catalyst

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 Catalyst testing
• 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

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 Catalyst testing
• 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
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 Catalyst testing
• 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

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 Catalyst testing
• Reactors above can be of different types
– Non-Stationary
• Batch
• Fed batch
• Transient
– Stationary/continuous
• Plug flow
• Fluidized bed
• Continuously stirred tank reactor

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 Catalyst testing
Laboratory reactors

Non-stationary Stationary

Fed- Fludized
Batch Transient Plug flow CSTR
Batch bed

Differential Integral

Single pass Recirculating

Internal External
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 Catalyst testing
• When measuring activity what do we get?
• The actual measured reaction rate differs from
the intrinsic reaction rate
• We get a reaction rate, but this may be
influenced by many things aside from the
chemical reaction
• Most of these may be traced to gradients
• The following discussion mainly concerns gas-
solid and liquid-solid reactions
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 Catalyst testing
• There are three types of gradients
– Gradients in the test reactor
• Axial
• Radial
• Wall effects
• Pressure drop
– Gradients between the bulk and the particles
• Temperature
• Concentration
– Gradients inside the particles
• Temperature
• Concentration
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 Catalyst testing

Lb
dp

dt

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 Catalyst testing
• For gas-solid operation of laboratory reactors:

Bed temperature gradients >

Temperature gradients between particles >
Concentration gradients inside the particles ~
Temperature gradients inside particles >
Concentration gradients between particles

• For liquid-solid operation the concentration gradients are

the most important
• This is due to the low heat conductivity of gas-solid fixed
beds and higher density, higher heat conductivity and lower
diffusivities in liquid-solid systems

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 Catalyst testing
• First determine minimum bed length to neglect effect
of axial dispersion:

𝐿𝑏 20𝑛 1
> ln
𝑑𝑝 𝐵𝑜 1−𝑥

• Where Bodensteins number is the Péclet number with

the particle diameter as characteristic dimension:
𝑢𝑑𝑝
𝐵𝑜 =
𝐷𝑎𝑥

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 Catalyst testing
Minimum bed length as a function of conversion
Gas phase
100

2 mm particles
Minimum bed lengths
Bed length (cm)

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calculated for different
1
0.1 mm particles conversion rates for two
particle sizes. Blue is first
0.1 order reaction and red
80 85 90 95 100
Conversion (%) second order.

Minimum bed length as a function of conversion

Liquid phase
1000

2 mm particles
Bed length (cm)

100

0.1 mm particles
10

1
80 85 90 95 100
Conversion (%) 19
 Catalyst testing
• For gaseous phase reactions, determine
minimum reactor diameter for neglecting wall
effects:
𝑑𝑡
> 10
𝑑𝑝
• For liquid-solid reactions determine maximum
reactor diameter for neglecting wall effects:
𝐿𝑏 𝐷𝑟𝑎𝑑 2𝐷𝑟𝑎𝑑
𝑑𝑡2 = =
𝜅 1 1
2𝑢𝑛 ln 𝑆𝑉𝑛 ln
𝜀 1−𝑥 1−𝑥
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 Catalyst testing
• We then determine the pressure drop in the
bed:
150𝜇𝑔 1 − 𝜀 2 1.75𝜌𝑔 1 − 𝜀 2
∆𝑃𝑏
= 𝑢+ 𝑢
𝐿𝑏 𝑑𝑝2 𝜀3 𝑑𝑝 𝜀 3

• And verify that it is below 20% of the total

pressure:
𝑃𝑡𝑜𝑡
< 0.2
𝐿𝑏

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 Catalyst testing
• The final reactor parameter to determine is the radial
temperature gradient:

𝑑𝑡2
−∆𝐻𝑟 𝑟𝑣,𝑜𝑏𝑠 1 − 𝜀 1 − 𝑏
𝐸𝑎 4 𝑥 1 + 1 𝑑𝑝 < 0.05
𝑅𝑇𝑤 𝜆𝑒𝑓𝑓,𝑏 𝑇𝑤 8 𝐵𝑖𝑤 𝑑𝑡

• To neglect the radial temperature gradient, the

expression above should < 5%
• The Biot number is the relation between the
conductivity in the bed and through the wall:
ℎ 𝑤 𝑑𝑝
𝐵𝑖 =
𝜆𝑒𝑓𝑓
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 Catalyst testing
Fluid flow
Porous catalyst particle
Concentration
in bulk

2 1 Exothermal
3
5 6 7 reaction
4

Temperature
in bulk
Stagnant
boundary layer

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 Catalyst testing
• Outer mass transfer negligible if:

𝑟𝑣,𝑜𝑏𝑠 0.05
′
<
𝑎 𝑘𝑓 𝑐𝑏 𝑛
• Outer heat transfer negligible if:

𝐸𝑎 −∆𝐻𝑟 𝑘𝑓 𝑐𝑏 𝑟𝑣,𝑜𝑏𝑠
′
< 0.05
𝑅𝑇𝑏 ℎ𝑇𝑏 𝑎 𝑘𝑓 𝑐𝑏
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 Catalyst testing
• Intraparticle mass transport negligible if:

𝑟𝑣,𝑜𝑏𝑠 𝐿2 𝑛 + 1
< 0.15
𝐷𝑒𝑓𝑓 𝑐𝑠 2
• Intraparticle heat transport negligible if:

𝐸𝑎 −∆𝐻𝑟 𝐷𝑒𝑓𝑓 𝑐𝑠 𝑟𝑣,𝑜𝑏𝑠 𝐿2

< 0.1
𝑅𝑇𝑏 𝜆𝑒𝑓𝑓,𝑝 𝑇𝑏 𝐷𝑒𝑓𝑓 𝑐𝑠
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 Catalyst testing
• The term:
𝑟𝑣,𝑜𝑏𝑠 𝐿2
𝐷𝑒𝑓𝑓 𝑐𝑠

• Is also known as Wheeler-Weisz modulus and is a function of the

effectiveness factor times Thiele modulus squared (ηø2)
• In the inner temperature gradient calculation:

−∆𝐻𝑟 𝐷𝑒𝑓𝑓 𝑐𝑠
𝜆𝑒𝑓𝑓,𝑝 𝑇𝑏

• Is abbreviated β and the next figure show the influence on the

reaction rate

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 Catalyst testing

The effectiveness factor and its relation to the Wheeler-Weisz modulus,

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 Catalyst testing
• Dilution a good way to handle gradients
– Improves heat transfer in bed
– Spread impact of reaction heat over larger volume
– Decrease effect of axial dispersion with higher bed
• Low surface area materials (quartz, α-alumina,
glass, SiC)
• May effect conversion, to neglect:

2.5𝑏𝑑𝑝
< 0.05
1 − 𝑏 𝐿𝑏

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 Catalyst testing
• The above given critera is a good indication
• The parameters required, especially for heat
conductivity, is difficult to estimate
• Recommended to verify experimentally
– Internal gradients by particle diameter
– External gradients by increasing flow rate

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FA0 FA0 FA0 FA0 FA10 FA20 FA30 FAn0

wn

Increasing w2 w3 Increasing
particle w1 flow rate
size with
constant
W/FA0
x1 x2 x3 xn x1 x2 x3 xn
Conversion

Conversion

Increasing particle diameter Increasing flow rate

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 Catalyst testing
• If temperature gradients in reactor is
suspected, dilute with inert heat conducting
material
• If change in conversion then gradients exist
• Activation energy may also be used to assess if
there are gradients

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Heterogeneous catalysis

Kinetic region: Ea
Intraparticle diffusion: Ea/2
Interphase mass transfer: about 8 kJ/mol

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 Conclusions
• Several reactor types available
• Make choice dependent on application
• Keep track of gradients in testing
• Try to avoid them or estimate them
• Make sure to perform experiments to verify
your calculations

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 Further reading
• J.R. Anderson, ”Introduction to Characterization and Testing of Catalysts”, AP, New York,
1985, 132-171
• D.E. Mears, Ind. Eng. Chem. Process. Develop., 10(4) (1971) 541-547
• D.E. Mears, Chem. Eng. Sci 26 (1971) 1361
• D.E. Mears, J. Catalysis, 20, 1971, 127
• D. Schweich, “Transport Effects – Heterogeneous”, Encyclopedia of Catalysis, E-bok,
2006
• C.N. Satterfield, ”Mass Transfer in Heterogeneous Catalysis”, M.I.T. Press, Cambridge,
1970
• G.F. Froment, and K.B. Bischoff, ”Chemical Reactor Analysis and Design”, John Wiley
Sons, New York, 1979
• Alpay and Kershenbaum, Chem. Eng. Sci. 50 (1995) 1063
• Weisz and Prater, Adv. Catal 6 (1954) 143
• E.E. Petersen, Chem. Eng. Sci. 17 (1962) 987
• K.B. Bischoff, Chem. Eng. Sci. 22 (1967) 525
• W.E. Stewart and J.V. Villadsen AIChE Journal 15 (1969) 28
• W. Goldstein and J.J Carberry, J. Catal. 28 (1973) 33
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 Further reading
• C.N. Satterfield, ”Heterogeneous Catalysis in Industrial Practice”, 2nd Ed., McGraw-
Hill Inc., New York, 1996, chapter 11
• J. Pérez-Ramirez et al., Catal Today 60 (2000) 93
• Sie, AIChE Journal 42 (1996) 3498
• Van Santen et al. ”Catalysis: an integrated approach”, 1999, p 417-431
• J.A. Moulijn et al. Catal. Today 11 (1991) 1
• F.J. Dumez and G.F. Froment, Ind. Eng. Chem. Process Des. Dev. 15 (1976) 291
• G. Dogu and T. Dogu, AIChE Journal 28 (1982) 1036
• A. Cybulski at al., Chem. Eng. Sci 230 (1975) 1015
• D. Kunii and O. Levenspiel, Ind. Eng. Chem. Res. 30 (1991) 136
• M.G. Freiwald and W.R. Paterson, Chem. Eng. Sci. 47 (1992) 1545
• R.J. Wijngaarden and K.R. Westerterp, Chem. Eng. Sci. 48 (1993) 1273
• C. Perego and S. Peratello, Catal. Today 52 (1999) 133
• J. van Klinken and R.H. van Dongen, Chem. Eng. Sci. 35 (1980) 59
• C.M. van den Bleek et al., Chem. Eng. Sci. 35 (1969) 681
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 Nomenclature
a’ Specific external surface area of Greek letters
catalyst particle (m2/m3)
ε Bed void fraction (-)
b Inert fraction of bed (-)
1-b Catalyst fraction of bed (-) η Effectiveness factor
c Concentration (mol/m3) ø Thiele modulus
dp Diameter of particle (m) κ Dimensionless number related to flow profile
dt Diameter of reactor tube (m) λ Thermal conductivity (J/(m*s*K))
Dax Diffusivity in axial direction (m2/s)
μ Dynamic viscosity (kg/(m*s))
Deff Effective diffusivity (m2/s)
Drad Diffusivity in radial direction ρ Density (kg/m3)
(m2/s) Φ Wheeler-Weisz modulus
Ea Activation energy (J/mol)
F Component flow (mol/s)
Subscript
h Gas-solid heat trasfer coefficient
(J/(m*s*K)) ax Axial
Hr Heat of reaction (J/mol) b Bed
kf Mass transfer coefficient (m/s) eff Effective
L Characteristic catalyst dimension
(m) g gas
Lb Bed length (m) p Particle
n Reaction order (-) rad Radial
P Pressure (Pa) s At external particle surface
R Gas law constant (J/(mol*K))
t Tube
rv, obs Observed volumetric reaction rate
(mol/(s*mp3) tot Total
SV Space velocity (s-1) w Wall
T Temperature (K)
u Linear velocity (m/s)
W Catalyst mass
x Conversion (-)

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 Thank you

Christian@Hulteberg.com
+46733969420

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