Chemical and Process Engineering Research www.iiste.

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Mass and Heat Transfer in Solid Catalyst Bed

Maya B. Mane 1 K.S.Kulkarni2 A.D.Kulkarni2
1.Student, Department of Chemical Engineering,Bharati Vidyapeeth Deemed University, College of Engineering,
Pune-411043, MS, India
2.Associate Professor ,Department of Chemical Engineering,Bharati Vidyapeeth Deemed University, College of
Engineering, Pune-411043, MS, India

Abstract
In heterogeneous catalysis much effort is put into the determination of the reaction kinetics. The primary of the
kinetic research is either to be able to optimize the design of a reactor or to gain more insight on the
fundamentals of a reaction. Since heterogeneous catalysis involves, by definition, at least two phases, exchange
of heat and mass between the phases is required for the reaction to take place. Due to these transport phenomena,
the observed rate at which the reaction takes place is not necessarily the same as its intrinsic rate, i.e. the unique
rate for a given catalyst at given conditions. Thus, when investigating the reaction kinetics in a laboratory-scale
catalytic reactor, one has to account for the factors that may generate a resistance to the reaction and that
disguise the intrinsic kinetics. In solid catalyst beds heat and mass transfer presented by equations for the
prediction of convective heat transfer, pressure drop, effective thermal conductivity and wall heat transfer
whereas under the conditions of radiant heat transfer may be neglected. It having various applications in
fluidized beds, packed beds, trickle beds, magnetically stabilized beds etc.
Keywords: Heterogeneous Catalysis, Mass Transfer, Heat Transfer, Catalyst Bed.

1.1 Introduction
Over the past 40 years, gas-liquid concurrent contacting in catalytic trickle bed reactors has achieved widespread
acceptance in a number of industrial applications. Although the down flow configuration is ubiquitous in the
petroleum and petrochemical industries. It is also effective for hosting other catalyst mediated reactions such as
for the production of commodity and specialty chemicals, pharmaceuticals and herbicides for waste treatment &
bio-scrubbing, in biochemical and electrochemical processing.
Gas–liquid reactions with heat and gas production are mainly analyzed with the model suggested by
Thiele. In this model, the chemical reaction in the porous catalyst is considered together with mass and heat
transfer, which is carried out by the molecular mechanism, i.e. liquid in pores has no forced convection. Such an
approach, however, cannot be applied for some reactions during which considerable quantities of gas or heat are
released. Indeed, in the case of the reaction with gas production, a gaseous compound remains in a soluble state
in liquid until the total pressure in a pore (equal to the sum of pressure in the reactor and pressure corresponding
to a soluble gaseous compound) exceeds the maximum possible pressure, which can be defined as the sum of the
outside and capillary pressures. If this occurs, a gas bubble will appear inside the pore.
Since there are many conditions under which a catalytic reaction can operate, it is to be expected that
these conditions may affect the mode of transport of gaseous molecules through the porous structure and, if the
rate of transport is comparable with the rate of chemical reaction, influence the observed kinetics. It is therefore
pertinent to consider the various modes of transport of gaseous molecules through the porous media. The rate at
which molecules diffuse through porous media is very much less than that associated with the translational
velocity of molecules. This is because molecules collide with the pore walls and with other molecules during
their passage through the catalyst structure, resulting in a completely random molecular motion. However, it is
sufficient to determine the net rate of molecular transport through an imaginary plane across which the
concentration gradient is known. This net rate will depend on the magnitude of the pore radius as compared with
the mean free path of the molecules and on whether or not there is a total pressure difference across the pore
length. We shall distinguish there are three types of mass transport in pores such as Knudsen flow, Bulk flow &
Forced flow.

1.2 Importance of Mass and Heat Transfer

1.2.1 Mass transfer in packed beds
When a gas flows through a packed bed of solid material, as it does in catalytic reactor, in addition to chemical
reaction mass is transferred by molecular diffusion and bulk flow. It is possible to write down differential
equations describing transport conditions within the bed by considering the conservation of mass within an
elementary volume element of the containing vessel.Suppose some solid material is packed in a cylindrical tube
of radius R and length L. Consider the mass entering and leaving volume as depicted in Fig. 1.

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Vol.33, 2015

Fig 1. Conservation of mass and heat within an elementary cylindrical volume.

This elementary volume is a cylindrical shell of thickness δR and length δz and is concentric with the cylinder
axis about which there is general symmetry. We assume that equimolar counter diffusion is occurring and write
down, in turn, the mass which is entering the volume longitudinally and radially in a time δt.

Mass entering by longitudinal bulk flow

ut2 RδRcz (1)
Mass entering by radial diffusion:
-De2πRδZ( )R (2)
Mass entering by longitudinal diffusion:
-De2πRδR( )z (3)
De is an effective diffusion coefficient, which, in general, will be different for the radial and longitudinal
directions, but is, herein, assumed the same. Next, the mass leaving this elementary volume in time δt is
accounted for.
Mass leaving by longitudinal bulk flow:
ut2 RδRcZ+δz = ut2 RδR{cZ + ( )zz} (4)
Mass leaving by radial diffusion:
²
-De2π(R+δR)δZ( ) R+δR=-De2π(R+δR)δZ{ ( )R+( )RδR} (5)
²
Mass leaving by longitudinal diffusion:
²
-De2πRδR( )Z+δZ=-De2πRδR{ ( )z+( )zδz} (6)
²

Consider, for the moment, that no chemical reaction occurs within the bed, and that mass is transferred by
equimolar counter diffusion only. The mass accumulating within the element in time δt is ( ⁄ ) 2πRδRδZ
and is equal to the algebraic sum of the quantities (1) to (6) inclusive entering and leaving the element.
Neglecting second order differences, the conversion equation therefore
² ²
=De{ }-ut (7)
² ²
The diffusivity De is really an effective diffusivity, for it embraces both molecular diffusion and eddy diffusion
by analogy with Boussinesq’s concept of eddy viscosity [1]. The overall rate of diffusion per unit area is given
by
N=-(D+ϵ) (8)
where D is the molecular diffusivity and ϵ the eddy diffusivity. Measurements and correlations of the effective
diffusivity have been made [2, 3] for catalysts as a function of the particle diameter dp and the tube diameter R.
the results were expressed in terms of a dimensionless group (Pe), the peclet number, which is given by uldp/ De.
For Reynolds numbers between 30 and 700 it was found that (Pe) is a particular function ƒ of the square of the
ratio of particle diameter to tube diameter,
(Pe)= = ƒ{( )2} (9)
2
Thus, for a given ratio of particle diameter to tube diameter, the function ƒ gives the Peclet number and hence
the effective diffusivity.
If, in addition to transport of matter by longitudinal and radial diffusion, chemical reaction occurs at a rate r(=kcn)
per unit reactor volume, the conservation equation becomes
² ²
= ( + kcn (10)
² ²
For a reaction in which there is a change in molar volume, the linear velocity will vary along the reaction path. In
this case equation (10) should be written

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Vol.33, 2015

² ²
= ( + kcn (11)
² ²

The steady-state solution to this equation has been found for certain conditions [4]. In particular, Vignes and
Trambouze [5] solved, by a numerical method, the equation for a second order reaction under isothermal
conditions. Laminar flow conditions were assumed and for all points in the reaction volume the concentration of
both reactants equated. A similar approach for isothermal catalytic reactions is possible. Baron, Manning and
Johnstone [6] studied the isothermal catalytic oxidation of SO2 by coating the wall of a reactor tube with a
vanadium pentoxide catalyst. In this case they neglected longitudinal diffusion. Since no chemical reaction
occurred within the volume of the tube, but only at the tube wall, for plug type flow the appropriate steady state
equation is
²
(12)
²
with the boundary conditions
c=c0 at z=0 for all values of R (13)
=0 at R=0 for all values of z (14)

= at R=d/2 for all values 0 < z < L (15)

e
where d and L are the tube diameter and length respectively. The boundary condition represented by equation
(15) arises because, at the tube wall, chemical reaction is exactly balanced by diffusion. The solution may be
accomplished analytically by using the laplace transform operator method. The result is an equation giving c in
terms of an infinite series containing the two independent variables z and R.
In catalytic reactors conditions are very often non-isothermal, so the steady state solution of equation (12)
1 !" #
²
(16)
²
is required in conjunction with an equation for heat conservation. The solution of the simultaneous equations is
accomplished by standard numerical methods and gives the concentration of reactant as a function of the two
independent variables corresponding to radial position and length. If the reactor is a narrow tube, the change in
concentration from axis to tube wall at any given position will be small, especially if the bulk flow rate is high.
Under the circumstances equation (16) reduces and is therefore to be regarded as an equation for use whenever
diffusion mass transfer in a direction perpendicular to flow is concomitant with a steady state chemical reaction.
The complete solution of an equation such as (10) in conjunction with an analogous equation for heat transfer
will given an indication of stability in packed beds.
1.2.2 Heat transfer in packed beds
Because the rate of a chemical reaction is an exponential function of temperature it is obvious that the
conversion of reactant is very much influenced by heat transferred to or from the wall of the reactor and heat
released during reaction. Furthermore, it is not always possible or even desirable, to operate chemical reactors
under isothermal conditions. The highly exothermic nature of some reactions may enhance either the reaction
rate, or the equilibrium yield, or both. For such reactions it is better for the heat of reaction to be absorbed by the
reactants, as would be the case in a reactor operated adiabatically. Some reactions are so exothermic that the
temperature increase over the first portion of the reactor length may be such that the catalyst activity is impaired.
A compromise between adiabatic and isothermal operation is made in these circumstances.
By analogy with mass transfer effects in packed beds, a general equation for heat transfer may be
deduced. Referring to Fig 1, an equation for the conservation of heat within an elementary cylindrical volume is
deduced as follows:
Heat entering element by longitudinal flow:
ρulcp2 π RδR(T-TO)Z (17)
Heat entering by radial conduction:
$
-ke2πRδz( )R (18)
Heat entering by longitudinal conduction:
$
-ke2πRδR( )z (19)
Heat out of element by longitudinal flow:
ρulcp2 π RδR(T-TO)Z+δz (20)
Heat out by radial conduction:
$
-ke2π(R+δR)δz( )R+ δR (21)

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Heat out by longitudinal conduction:

$
-ke2πRδR( )z+ δz (22)
Heat out by chemical reaction:
-2πRδRδzr∆H (23)
ρ is the gas density, cp the specific heat at constant pressure and ke the effective thermal conductivity of the bed
assumed the same in both longitudinal and radial directions. T0 is any arbitrary temperature to which the heat
content of the system may be referred. The heat accumulating within the element is calculated by defining a
mean specific heat (cp)m and a mean density ρm. The heat capacity of the system is then given by
(cp)m ρm= cpρΨb+(cp)sρs(1-Ψ), (24)
where Ψb is the void space per unit reactor volume. The subscript s refers to the solid. The resulting equation for
the conservation of heat is then
$ ²$ $ ²$ $
(cp)m ρm = k e( + + )- ρulcp -r∆H (25)
² ²
Because this is more than one mechanism by which heat may be transferred within the packed bed, ke
is a property of the system which depends on variables such as temperature, gas flow rate, particle diameter and
porosity, and the thermal conductivity of gas and solid. In fact, ke will, in general, depend on radial position, and
an additional term ke/ %) &/ %) must then be added to the right hand side of equation (25).
For most design problems the steady state solution of equation (25) it required,
$ ²$ $
ρulcp = k e( + -r∆H (26)
²
This latter equation represents an approximation, since the temperature of the gas and the solid are
assumed identical at every point in the reactor volume. If gas and solid temperatures differ, the procedure is to
write an energy balance equation for the gas and for the solid and then solve the two resulting simultaneous
partial differential equations numerically. Considerable simplification results if the gas is sufficiently well mixed
for the gas temperature Tg to be constant over any given cross-section. Then only the conservation equation for
the solid need be considered, but this will involve an additional term due to a quantity of heat kg2π RδRδz(T-Tg)
transferred from the gas.
Wilhelm and co-workers [7] have discussed the solution for a case in which longitudinal heat transfer
is neglected and the heat liberated by chemical reaction is considered to be a linear function of temperature. The
conservation equation which Wilhelm obtained is
²$ $
к e( + -kg(T-Tg)+(α+βT)=0 (27)
²

the last bracketed term representing the heat liberated by reaction. The kinetic coefficients α and β may be found
from separate experiments designed specifically to examine the reaction rate. The effective thermal conductivity
кe, and the heat transfer coefficient kg (based on the reactor volume), can be found from experiments in which the
reactor tube is packed with inert material having similar thermal properties to the catalyst. Equation (27) may be
reduced to a Bessel equation of order zero and may thus be solved analytically for a particular set of boundary
conditions.
When it is safe to ignore the variation in temperature across the tube radius, a fairly simple approach to the
problem of heat transfer is possible. An equation for the conservation of energy may be written by considering
an elementary section, thickness δz, of the tube of cross sectional area Ac. the surface area of the wall per unit
length will be 2 Ac/Aw. therefore the amount of heat exchanged with surroundings is:
kwAw(Tm-Tw)δz (28)
where Tm is the mean temperature over the cross section, Tw is the wall temperature and kw a heat transfer
coefficient.
The heat produced by reaction in the element is:
-∆Hr Ac δz (29)
where r is the reaction rate and ∆H the enthalpy of reaction. The energy balance is therefore
∑micpδT= kwAw(Tm-Tw)δz--∆Hr Ac δz (30)
where the summation on the left of the equation represents the net increase in enthalpy of all the components of
the reaction mixture. Finally, a rate equation such as
F δX=rAc δz (31)
must be written. These simultaneous equations can be solved by standard numerical procedures. If the reactor is
adiabatic, then no heat is exchanged with the surrounding and the energy conservation equation is
-∆Hr Ac δz = F ∆H δX = ∑micpδT (32)
In this case the solution is simpler, since a relation between temperature and conversion is first found, and then
equation (32) subsequently integrated.

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1.3 Applications
Knowledge of the particle to liquid heat and mass transfer coefficients in trickle beds is important. Particularly in
contexts where exothermic reactions impede liquid replenishment over dried spots in the catalyst bed, or when
the transport, especially in liquid limited reactions, is curbed by excessive liquid-solid interfacial resistance.
Although particle liquid-heat and mass transfer coefficients in trickle beds are linked to each other, the known
Chilton-Colburn analogy or similar failed to yield. A single Nu/Sh correlation to quantify both heat and mass
transfer phenomena at the pellet scale. In this work, a single correlation embedding the heat and mass transfer
information into a peclet number was derived and validated over 1259 particle-liquid heat and mass transfer
coefficients in trickle beds. Depending on wheather a heat or mass peclet number was used, the proposed
correlation predicted Nu and Sh numbers with average absolute relative error of 18 and 22%, respectively. In
particular, when equal heat and mass peclet numbers occur, under physically and geometrically similar
conditions, the correlation predicts true analogy between heat and mass transfer at the pellet level [8].
A theoretical analysis of thermal processes in liquid–gas exothermic reactions in a porous catalyst
shows the existence of the alternating motion of liquid in the pore. According to this model, if the released heat
in the pore exceeds a certain critical value, the alternating motion of the liquid driven by the formation of the
bubble takes place in the pore. Specifically, because of the heating of the liquid in the pore, the partial pressure
of vapor saturated in liquid increases until the total pressure of the saturated gas and vapor becomes greater than
the maximum possible pressure in the pore (equal to the sum of capillary pressure and pressure in the reactor)
and the bubble thereby comes into being. The growing bubble pushes the liquid out of the pore. Since the
reagent(s) is no longer in the pore, the reaction ceases and the generated heat dissipates. The liquid penetrates
into the pore due to capillary force and the process of bubble formation occurs once again. A detailed analysis of
this non-stability is undertaken. This paper seeks to show how this theory can explain some dependencies of the
reaction rate observed in practice, mass and heat transfer in the fixed and suspended catalyst as well as some
practical recommendations for catalyst development and process intensification. Analogy between oscillation
behaviour and the boiling process is considered [9].
The theoretical analysis of liquid and gas behaviour in catalyst pores in chemical reactions producing a
gas phase shows the existence of pulsating, oscillating movements of liquid in pores. The necessary conditions
for the occurrence of such oscillations are defined. Influences of oscillation behaviour on the chemical rate as
well as its possible influence with regard to increasing mass transfer are discussed. Analysis and illustration of
this kind of reactions are carried out using the results of hydrogen peroxide decomposition on CuCr catalyst
[Chem. Eng. Sci. 51 (1996) 2721] [10].
This article discusses the effects of extra- and intraparticle mass and heat transfer in transient
experiments over heterogeneous catalysts. To this purpose, the time-dependent transport in a catalyst particle
when introducing a reactant in an inert gas phase has been analyzed. The analysis has led to one criterion
assuring the absence of both extra- and intraparticle mass transfer limitations during steady-state experiments.
Furthermore, criteria for the absence of mass and heat transport limitations during transient experiments have
been developed by extending the criteria for the absence of mass and heat transport limitations during steady-
state experiments. As will be shown, transient kinetics are not affected by heat transfer as long as the steady-state
criteria for the absence of mass and heat transport limitations are fulfilled [11].

1.4 Conclusion
Mass and Heat transfer in packed beds have been considered. The differential equations describing transport
conditions within the bed by considering the conservation of mass and heat within an elementary volume
element of the containing vessel are recommended. Nu/Sh correlation for particle liquid heat and mass transfer
coefficients based on peclet similarity, Oscillations in pores of a catalyst particle and Analysis of heat processes
and their influence on chemical conversion, mass and heat transfer also recommended.

1.5 References
1) J. Boussinesq, Mem pres pres par div savants a 1’Acad Sci. Paris 23, 46 (1877).
2) R. A. Bernard and R. H. Wilhelm, Chem. Engng Progr. 46, 233 (1950).
3) R. W. Fuhien and J. M. Smith, A. I. Ch. E. Jl. 1, 28 (1955).
4) T. Baron, Chem. Engng Progr. 48, 118 (1952).
5) J. P. Vignes and P. J. Trambouze, Chem. Engng Sci. 17, 73 (1962).
6) T. Baron, W. R. Manning and H. F. Johnstone, Chem. Engng Progr. 48, 125 (1952).
7) R. H. Wilhelm, W. C. Johnstone and F. S. Acton, Ind. Engng Chem. 35, 562 (1943).
8) F.Larachi, C. Alix, B. P. A. Grandjean and A. Bernis, Nu/Sh Correlation for particle liquid heat and mass
transfer coefficients in trickle beds based on Peclet Similarity.
9) Leonid B. Datsevich, Oscillations in pores of a catalyst particle in exothermic liquid (liquid–gas) reactions
Analysis of heat processes and their influence on chemical conversion, mass and heat transfer

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Vol.33, 2015

10) Leonid B. Datsevich, Some theoretical aspects of catalyst behaviour in a catalyst particle at liquid (liquid–
gas) reactions with gas production: oscillation motion in the catalyst pores.
11) F. H. M. Dekker and A. Bliek, F. Kapteijn and J. A. Moulijn, Analysis of mass and heat transfer in transient
experiments over heterogeneous catalysts.

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