Reactor Design for Hetergoneous Catalytic Reactions

Lecture # 01

KBK (ChE) Ch. 12 1 / 38

 Introduction Types of heterogeneous catalytic reactors

Commercially significant reactors

1 Reactors in which the solid catalyst particles remain in fixed positions

relative to one another (fixed bed, trickle bed, and moving bed
reactors)

2 Reactors in which the particles are suspended in a fluid and are

moving about constantly (fluidized bed and slurry reactors).

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 Introduction Types of heterogeneous catalytic reactors

Fixed bed reactors

also known as packed bed reactors

regarded as the workhorse of the chemical industry with respect to

the number of reactors employed and the economic value of the
materials produced

examples: Ammonia synthesis, sulfuric acid production (by oxidation

of SO2 to SO3 ), and nitric acid production (by oxidation of NH3 )

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 Introduction Types of heterogeneous catalytic reactors

Configurations of FBR

1 A single large bed

2 Multiple horizontal beds supported on trays arranged in a vertical

stack

3 Multiple parallel packed tubes in a single shell

4 Multiple beds each in its own shell

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 Introduction Types of heterogeneous catalytic reactors

Advantages of FBR

1 simplicity, and low costs for construction, operation and maintenance

2 no problem in separating the catalyst form the reactor effluent stream

3 a wide variation of space time can be used

4 for extremely high pressure or high pressure catalytic reactions usually

FBR is the only economic viable system

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 Introduction Types of heterogeneous catalytic reactors

Disadvantages of FBR

1 heat transfer to and from a large fixed bed of catalysts often

represents a significant problem

2 maintenance of uniform flow distribution in fixed bed reactors can be

a problem

3 minimum pellet size that can be used is restricted by the permissible

pressure drop through the bed. This might lead to diffusional
limitations

4 catalyst regeneration or replacement is relatively difficult to approach

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 Introduction Types of heterogeneous catalytic reactors

Trickle bed reactors

primary uses of trickle bed reactors- hydrodesulfurization, hydrocracking,

and hydrotreating of various high-boiling petroleum fractions
Ranade et all, Trickle bed reactors: reactor engineering & applications, Elsevier, 2011
KBK (ChE) Ch. 12 7 / 38
 Introduction Types of heterogeneous catalytic reactors

Advantages of TBR

1 The direct and capital costs are significantly less for trickle bed
operation than for an equivalent hydrodesulfurization unit operating
entirely in the vapor phase

2 The use of this reactor type makes it possible to process feedstocks

with such high boiling points that straight vapor-phase operation
would lead to excessive undesirable side reactions

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 Introduction Types of heterogeneous catalytic reactors

Disadvantages to TBR

1 nature and extent of the liquid distribution within the catalyst bed
vary drastically with changes in the liquid and vapor flow rates, the
properties of the reaction mixture (especially its viscosity and wetting
characteristics), and the design of the reactor (especially the liquid
distribution system)

2 either external or intraparticle mass transfer effects are significant in

trickle bed reactors

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 Introduction Types of heterogeneous catalytic reactors

Moving bed reactors

In catalytic cracking where catalyst deactivation is so rapid that fixed beds

must be regenerated after only a few minutes of time on stream, moving
bed reactor is a good option

Salmi et all, Chemical Reaction Engineering and Reactor Technology, CRC Press, 2011
KBK (ChE) Ch. 12 10 / 38
 Introduction Types of heterogeneous catalytic reactors

Disadvantages of MBR

1 It is necessary to design special control valves to provide proper solids

flow and to maintain close control over the solids level within the
reactor

2 care must be taken in the design of these reactors to prevent

bypassing of the bed by the fluid reactant stream and to ensure good
distribution of the solids at all levels

3 When catalyst decay is slow, so that fixed bed operation is

satisfactory with infrequent shutdown for catalyst regeneration,
moving bed operation does not offer a viable alternative

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 Introduction Types of heterogeneous catalytic reactors

Fluidized bed reactors

Fluidized bed reactors were first employed on a large scale for the catalytic
cracking of petroleum fractions, but more recently they have been
employed for an increasingly large variety of reactions, both catalytic and
non-catalytic

the catalyst particles used in fluidized bed operations have dimensions in

the range of 10 to 300 m. For optimum fluidization, it is important to
employ the proper particle size distribution

Typically, height/diameter ratios of 2 : 1 or greater are employed. Large

systems are required in part to accommodate heat transfer equipment,
cyclone separators, and other internal equipment.

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 Introduction Types of heterogeneous catalytic reactors

Advantages of FBR

1 uniform temperature can be maintained throughout the catalyst bed

2 it permits continuous, automatically controlled operations using

reactant-catalyst systems that require catalyst regeneration at very
short intervals

3 it leads to more efficient contacting of gas and solid than many

competitive reactor designs

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 Introduction Types of heterogeneous catalytic reactors

Disadvantages of FBR

1 cannot be used with catalyst solids that will not flow freely or that
have a tendency to agglomerate

2 solids collection systems, including cyclone separators and

electrostatic precipitation, must often be provided to minimize
catalyst losses and contamination of the environment

3 it leads to a larger pressure drop than fixed bed operation with

concomitant higher operating costs

4 Fluidized bed operations also have the disadvantage that the fluid
flow deviates markedly from plug flow, and the bypassing of solids by
bubbles can lead to inefficient contacting
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 Introduction Types of heterogeneous catalytic reactors

Slurry reactors

Whitaker and Cassano, Concepts and Design of Chemical Reactors, CRC Press, 1986
KBK (ChE) Ch. 12 15 / 38
 Introduction Types of heterogeneous catalytic reactors

Advantages of SR
1 A well-agitated slurry may be kept at a uniform temperature
throughout, eliminating hot spots
2 The high heat capacity associated with the large mass of liquid
facilitates control of the reactor and provides a safety factor for
exothermic reactions that might lead to thermal explosions or other
runaway events
3 Because liquid phase heat transfer coefficients are large, heat recovery
is practical with these systems
4 The small particles used in slurry reactors may make it possible to
obtain much higher rates of reaction per unit weight of catalyst than
would be achieved with the larger pellets
5 continuous regeneration of the catalyst can be obtained by
continuously removing a fraction of the slurry from which the catalyst
is then separated, regenerated, and returned to the reactor
6 possible to use catalysts that are difficult or impossible to pelletize
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 Introduction Types of heterogeneous catalytic reactors

Disadvantages of SR

1 Solubilization and mass transfer processes may influence observed

conversion rates, and these factors may introduce design uncertainties
2 roblems of developing mechanical designs that will not plug up and of
selecting carrier liquids in which the reactants are soluble, yet which
remain stable at elevated temperatures in contact with reactants,
products, and the catalyst
3 the ratio of liquid to catalyst is much greater than in a trickle bed
reactor. Hence, the relative rates of undesirable homogeneous liquid
phase reactions will be greater in the slurry reactor, with a potentially
adverse effect on the process selectivity

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 Mass transfer within porous catalysts Some basic terminologies

Ordinary Diffusion

Diffusion when the mean free path of a molecule is small compared with
the diameter of the pore

At 1 atm the mean free path of typical gaseous species is on the order of
105 cm or 103 .

In pores with diameters larger than 104 cm, the mean free path is much
smaller than the diameter, and collisions with other gas-phase molecules
will occur much more often than collisions with the pore walls

Under these circumstances, ordinary bulk diffusion coefficients may be

used with Ficks first law to evaluate the rate of mass transfer and the
concentration profile in the pore
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 Mass transfer within porous catalysts Some basic terminologies

Knudsen diffusion

occurs when the mean free path between collisions is large compared with
the pore diameter

This situation prevails when the gas density is low or when the pore
dimensions are very small

The gas flux is reduced by the wall resistance.

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 Mass transfer within porous catalysts Some basic terminologies

Relative contribution and Combined diffusivity

By comparing the relative magnitudes of the mean free path () and the
pore diameter (2r ), it is possible to determine whether bulk diffusion or
Knudsen diffusion may be regarded as negligible

Using the principles of the kinetic theory of gases, it can be shown that:
DAB
=
2r DK

there will be a range of pressures or molecular concentrations over which

the transition from ordinary molecular diffusion to Knudsen diffusion takes
place. Within this region both processes contribute to the mass transport,
and it is appropriate to utilize a combined diffusivity (Dc )

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 Mass transfer within porous catalysts Some basic terminologies

Combined diffusion
The combined diffusivity is defined as the ratio of the molar flux to the
concentration gradient, irrespective of the mechanism of transport

For species A the correct form for the combined diffusivity is the following:
1
Dc =
[1/DK ] + [(1 YA )/DAB ]

where:
NA
=1+
NB
For equimolal counterdiffusion, NB = NA and therefore:
1
Dc =
[1/DK ] + [1/DAB ]

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 Mass transfer within porous catalysts Some basic terminologies

Surface diffusion

An adsorbed species may be transported either by desorption into the gas

phase or by migration to an adjacent site on the surface. It is this latter
phenomenon that is referred to as surface diffusion

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 Mass transfer within porous catalysts Some basic terminologies

Limitation and Effective diffusivity

the various types of diffusion has presumed that the diffusion takes place
in a well characterized pore structure, that is, straight cylindrical pores

the catalysts used in industry have extremely complex structures with

interconnecting pores, tortuous pores, and wide variations in pore diameter
as one moves along the length of the pore

we need to convert the combined diffusivity into effective diffusivity which

are required for use in systems of unspecified pore geometry

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 Mass transfer within porous catalysts Some basic terminologies

Effective diffusivity

Effective diffusivity is a transport coefficient that pertains to a porous

material in which the calculations are based on total area (void plus solid)
normal to the direction of transport, rather than the void area alone.

The effective diffusivity accounts for the fact that:

1 Not all of the area normal to the direction of the flux is available for
the molecules to diffuse
2 the paths are tortuous
3 the pores are of varying cross-sectional areas
Equation relating effective diffusivity to combined diffusivity:
Dc p Dc p
Deff = =
L0 S 0 0

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 Mass transfer within porous catalysts Some basic terminologies

Pore constriction and pore tortuosity

actual distance a molecule travels between two points

tortuosity =
shortest distance between these two points
tortuosity
tortuosity factor =
constriction factor

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 Mass transfer within porous catalysts Some basic terminologies

Measuring effective diffusivity

hypothetical estimates of effective diffusivities are not adequate for

accurate design calculations and recourse must be made to experimental
methods to evaluate these parameters

Approach one - by measuring counter diffusion rates

Approach two - efflux method

A third approach

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 Mass transfer within porous catalysts Some basic terminologies

Effectiveness factor

the effectiveness factor is the ratio of the actual reaction rate to that
which would be observed if the total surface area throughout the catalyst
interior were exposed to a fluid at the same conditions (composition,
temperature, etc.) as those prevailing at the outside surface of the particle

measured rate for entire catalyst particle

=
rate evaluated at exterior surface conditions for entire particle

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 Mass transfer within porous catalysts Some basic terminologies

Thiele modulus

Thiele modulus, a dimensionless quantity, is a measure of the rate of the

catalytic reaction relative to the rate of diffusion of the reactants in the
pores of the catalyst (internal mass transfer)

low values correspond to situations with high rates of internal mass

transfer and high values to situations where internal mass transfer
determines the effective rate of reaction.

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 Mass transfer within porous catalysts Some basic terminologies

Relationship between effectiveness factor and Thiele

modulus

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 Mass transfer within porous catalysts Some basic terminologies

Reaction kinetics and effectiveness factor

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 Mass transfer within porous catalysts Some basic terminologies

Mass transfer between the bulk fluid and external catalyst

surface

In some cases, a significant concentration difference arises as a

consequence of physical limitations on the rate at which reactant
molecules can be transported from the bulk fluid to the exterior surface of
the catalyst particle

Table 12.1 - Correlations for Mass Transfer Factors in Packed Beds

Table 12.2 - Correlations for Mass and Heat Transfer Factors in Fluidized
Beds

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 Mass transfer within porous catalysts Some basic terminologies

Global reaction rate

Global rate expression that takes into account the influence of physical
transport processes on the rate at which reactants are converted to
products

Global rate expressions then include both external heat and mass transfer
effects on the reaction rate and the efficiency with which the internal
surface area of a porous catalyst is used

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 Mass transfer within porous catalysts Some basic terminologies

reactant concentration profiles in various global rate

regimes

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 Design of Fixed Bed Reactors

One/two dimensional models

One dimensional models take into account variations in composition and

temperature along the length of the reactor

two dimensional models also allow for variations of composition and

temperature properties in the radial direction

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 Design of Fixed Bed Reactors

Pseudo homogeneous model

The pseudo homogeneous model assumes that the reactions are taking
place throughout the reactor volume, not as localized at the catalyst
surface

The rate expressions for use with these models are obtained by taking the
product of the global reaction rate per unit mass of catalyst and the bulk
density (B ) of the catalyst:

rv = rm B

The units of rV are moles converted/(volume.time), and rV plays a role

similar to the rates employed in homogeneous reactor design
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 Design of Fixed Bed Reactors

Heterogeneous model

Heterogeneous models of fixed bed reactors account explicitly for the

presence of the solid catalyst by writing material and energy balance
equations for both the solid and fluid phases

The basic heterogeneous model considers only transport by plug flow, but
differentiates between bulk fluid properties and those prevailing at the
external surface of the catalyst pellet

Models may also be developed that allow for intraparticle gradients and for
radial variations in system properties

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 Design of Fixed Bed Reactors

The One Dimensional Pseudo Homogeneous Model of

Fixed Bed Reactors

The one dimensional model assumes that species concentrations and fluid
temperature vary only in the axial direction

The one dimensional model provides a rapid means of (1) obtaining an

estimate of the reactor size necessary to achieve a given conversion, and
(2) examining the influence of several design variables on the behavior of
the reactor

the model provides no information concerning the possibility of achieving

an excessive temperature at the center of the tube that may be markedly
different from the mean temperature at the same longitudinal position.
Such temperatures may be unacceptable for reasons of reactor stability,
process selectivity, or catalyst deactivation

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 Design of Fixed Bed Reactors

The Two Dimensional Pseudo Homogeneous Model of

Fixed Bed Reactors

Experimental measurements indicate that the fluid temperature and

composition are not uniform across a section of the tube normal to the
flow.

Whenever there is extensive heat exchange between the packed bed

reactor and its surroundings, one requires at least a two dimensional model
to simulate the reactor performance

A complete two dimensional model would account for the radial

distribution of velocity, for the radial concentration and temperature
gradients , and for axial dispersion of heat and mass.

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