CRE-II - Chapter-04 Fluid-Particle Systems - HKB 2.10.18

Chemical Reaction Engineering –II
(2170501)
Chapter-04: Fluid-Particle
systems
Hemant Kumar Balsora
Chemical Engineering Department,
[email protected]
Fluid-Particle systems : Introduction
Gas solid Liquid solid

system system
Chapter-04:
Fluid-Particle Reactions: Kinetics
Class of heterogeneous reactions in which a gas or liquid
contacts a solid, reacts with it, and transforms it into product
Such reactions may be represented by
Figure: Different sorts of behavior of reacting solid particles (octave page-567)
Solid particles remain unchanged in size during reaction when
they contain large amounts of impurities which remain as a
nonflaking ash or if they form a firm product material by the
reactions of Eq. 2 or Eq. 3.
Particles shrink in size during reaction when a flaking ash or
product material is formed or when pure B is used in the
reaction of Eq. 1
Fluid-solid reactions are numerous and of great industrial
importance. Those in which the solid does not appreciably
change in size during reaction are as follows:
The roasting (or oxidation) of sulfide ores to yield the metal
oxides
Still other examples are the dissolution reactions, the attack of metal chips by
acids, and the rusting of iron.
Observations
Particle size remain unchanged

in process
Particle shrink during process
(unreacted-core)
SELECTION OF A MODEL
We should clearly understand that every conceptual picture or
model for the progress of reaction comes with its
mathematical representation, its rate equation.
Consequently, if we choose a model we must accept its rate
equation, and vice versa.
If a model corresponds closely to what really takes place, then
its rate expression will closely predict and describe the actual
kinetics;
if a model differs widely from reality, then its kinetic
expressions will be useless
For the noncatalytic reaction of particles with surrounding

fluid, we consider
Progressive-Conversion Model (PCM).
Here we visualize that

reactant gas enters and
reacts throughout the
particle at all times, most
likely at different rates at
different locations within
the particle.
Thus, solid reactant is
converted continuously
and progressively
throughout the particle
as shown in Fig. 25.2.
(octave)
Shrinking-Core Model (SCM)
Here we visualize that

reaction occurs first at the
outer skin of the particle.
The zone of reaction then
moves into the solid, leaving
behind completely
converted material and inert
solid. We refer to these as
"ash.“
Thus, at any time there

exists an unreacted core of
material which shrinks in
In examining the cross section of partly reacted solid particles, we
usually find unreacted solid material surrounded by a layer of ash.
The boundary of this unreacted core may not always be as sharply

defined as the model pictures it; however, evidence from a wide
variety of situations indicates that in most cases the shrinking-core
model (SCM) approximates real particles more closely than does
the progressive conversion model (PCM).
Observations with burning coal, wood, briquettes, and tightly

wrapped newspapers also favour the shrinking-core model.
Since the SCM seems to reasonably represent reality in a wide
variety of situations, we develop its kinetic equations in the
following section.
In doing this we consider the surrounding fluid to be a gas.

SHRINKING-CORE MODEL FOR SPHERICAL PARTICLES OF
UNCHANGING SIZE
This model was first developed by Yagi
and Kunii (1955, 1961),who visualized
five steps occurring in succession
during
Step reaction of
1. Diffusion (see Fig. 25.4).
gaseous reactant A
through the film surrounding the particle
to the surface of the solid.
Step 2. Penetration and diffusion of A
through the blanket of ash to the surface
of the unreacted core.
Step 3. Reaction of gaseous A with solid at

this reaction surface
Step 4. Diffusion of gaseous products
through the ash back to the exterior
surface of the solid.
Diffusion Through Gas Film Controls
Noting from the stoichiometry of Eqs. 1,2, and 3 that dNB = bdNA,
If we let𝝆B, be the molar density of B in the solid and V be the volume of a particle, the
amount of B present in a particle is
The decrease in volume or radius of unreacted core accompanying the
disappearance of dNB moles of solid reactant is then given by
Replacing Eq. 6 in 4 gives the rate of reaction in terms of the shrinking radius
of unreacted core, or
where kg is the mass transfer coefficient between fluid and particle Rearranging and
integrating, we find how the unreacted core shrinks with time. Thus,
This can be written in terms of fractional conversion by noting that
Therefore
Thus we obtain the relationship of time with radius and with conversion
Diffusion through Ash Layer
Controls
Consider a partially reacted particle
as shown in Fig. 25.6
Both reactant A and the boundary of the
unreacted core move inward toward the
center of the particle
But for GIS systems the
shrinkage of the unreacted core is
slower than the flow rate of A
toward the unreacted core by a
factor of about 1000,
Which is roughly the ratio of
densities of solid to gas
Because of this it is reasonable
for us to assume, in considering
the concentration gradient of A in
the ash layer at any time, that the
unreacted core is stationary
For GIS systems the use of the steady-state
assumption,
Integrating eqn (3) across the ash layer form R to rc,
we obtained
For convenience, let the flux of A within the ash

layer be expressed by Fick's law for equimolar
counter diffusion, we have
where De is the effective diffusion coefficient

of gaseous reactant in the ash layer.
Combining Eqs
This expression represents the conditions of
a reacting particle at any time.
In the second part of the analysis we let the size
of unreacted core change with time. For a given
size of unreacted core, dNA/dt is constant;
however, as the core shrinks the ash layer
becomes thicker, lowering the rate of diffusion
of A.
A+bB
Multiplied by 6
For the complete conversion of a particle,
rC = 0, and the time required is
This can be written in terms of fractional

conversion by noting that
Equation (9) is the final expression when diffusion

though ash layer controls
Chemical Reaction
Controls
Chemical Reaction
Controls
Figure 25.7 illustrates concentration gradients
within a particle when chemical reaction controls.
Since the progress of the reaction is unaffected by the
presence of any ash layer, the rate is proportional to
the available surface of unreacted core.
Thus, based on unit surface of
unreacted core, rc, the rate of reaction
for the stoichiometry of Eqs. 1, is
A+bB
A+bB
The time τ required for complete
conversion is given when rc = 0, or
The decrease in radius or increase in fractional

conversion of the particle in
terms of r is found by combining Eqs. 3 and 4 Thus,
Limitations of the Shrinking Core Model
The assumptions of this model may not match reality precisely.
For example, reaction may occur along a diffuse front rather than along a sharp
interface between ash and fresh solid, thus giving behavior intermediate between
the shrinking core and the continuous reaction models. This problem is
considered by Wen (1968), and Ishida and Wen (1971).
Also, for fast reaction the rate of heat release may be high enough to cause
significant temperature gradients within the particles or between particle and the
bulk fluid. This problem is treated in detail by Wen and Wang (1970).
Despite these complications Wen (1968) and Ishida et al. (1971), on the
basis of studies of numerous systems, conclude that the shrinking core
model is the best simple representation for the majority of reacting
gas-solid systems.
There are, however, two broad classes of exceptions to this conclusion. The
first comes with the slow reaction of a gas with a very porous solid. Here
reaction can occur throughout the solid, in which situation the continuous
reaction model may be expected to better fit reality. An example of this is the
slow poisoning of a catalyst pellet.
The second exception occurs when solid is converted by the action of heat,
and without needing contact with gas. Baking bread, boiling missionaries, and
DETERMINATION OF THE RATE-CONTROLLING STEP
The kinetics and rate-controlling steps of a fluid-solid reaction are deduced by

noting how the progressive conversion of particles is influenced by particle size
and operating temperature. This information can be obtained in various ways,
depending on the facilities available and the materials at hand.
Temperature. The chemical step is usually much more temperature-sensitive
than the physical steps; hence, experiments at different temperatures should
easily distinguish between ash or film diffusion on the one hand and chemical
reaction on the other hand as the controlling step.
Time. Figures 25.9 show the progressive
conversion of spherical solids when
chemical reaction, film diffusion, and ash
diffusion in turn control. Results of
kinetic runs compared with these
predicted curves should indicate the rate
controlling step. Unfortunately, the
difference between ash diffusion and
chemical reaction as controlling steps is
not great and may be masked by the
scatter in experimental data.
Particle Size. Equations of time required for specific conversion level is
depended on the particle size , show that the time
needed to achieve the same fractional conversion for particles of different
but unchanging sizes is given by
Thus kinetic runs with different sizes of particles can distinguish between reactions
in which the chemical and physical steps control.
Ash Versus Film Resistance. When a hard solid ash forms during reaction, the
resistance of gas-phase reactant through this ash is usually much greater than
through the gas film surrounding the particle. Hence in the presence of a nonflaking
ash layer, film resistance can safely be ignored. In addition, ash resistance is
unaffected by changes in gas velocity
Predictability of Film Resistance. The magnitude of film resistance can be
estimated from dimensionless correlations such as Eq. (A). Thus an observed rate
approximately equal to the calculated rate suggests that film resistance controls
Eq. (A).
Example 1: A batch of solids of uniform size is treated by gas in a
uniform environment. Solid is converted to give a non-flacking
product, according to shrinking core model. Conversion is 7/8 for the
reaction time of 1 hr, conversion is 100% in 2 hrs. Which mechanism
is rate control?
Example -2 : Spherical particles of zinc blend of size R = 0.05 mm are roasted in a 10%
oxygen stream at 900 oC and 1 atm. The reaction stoichiometry of reaction is
2ZnS + 3O2 → 2ZnO + 2SO2
Assuming reaction proceeds by shrinking core model and gas film resistance is negligible,
calculate the time needed for complete conversion of particle and relative resistance of ash
layer diffusion during this operation
Data: Density of solid = 4.13 gm/cm3, Reaction rate constant ks = 2 cm/sec, De = 0.08
cm2/sec
Example -3 : Calculate the time required for complete combustion of spherical particles of
graphite (radius 12 mm, bulk density 2.4 g/cm3, ) in 12% oxygen stream at 900 oC and 1 atm
. Assume gas film resistance to be negligible
Data: Reaction rate constant ks = 25 cm/sec,
Ans : 7699.8 seconds

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Chemical Reaction Engineering –II

Gas solid Liquid solid

Particle size remain unchanged

For the noncatalytic reaction of particles with surrounding

Here we visualize that

Here we visualize that

Thus, at any time there

The boundary of this unreacted core may not always be as sharply

Observations with burning coal, wood, briquettes, and tightly

In doing this we consider the surrounding ﬂuid to be a gas.

Step 3. Reaction of gaseous A with solid at

For convenience, let the flux of A within the ash

where De is the effective diffusion coefficient

This can be written in terms of fractional

Equation (9) is the final expression when diffusion

The decrease in radius or increase in fractional

The kinetics and rate-controlling steps of a fluid-solid reaction are deduced by

Ans : 7699.8 seconds

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