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range from 30-60% and most of the energy is lost in the flue gases, through the kiln shells
and as heat in the product (2). Improving the energy efficiency of a lime kiln, not only
reduces greenhouse gas emissions, but also has significant impact on the cost of producing
lime. Understanding lime calcination kinetics has the potential to aid identification of energy
reduction and energy efficiency opportunities.
An energy audit, carried out at Perry Lime Ltd, established the distribution of energy use in
a lime kiln process as illustrated in Figure 1. The process was a typical quarry limestone
processing facility with a conventional Rotary Kiln. The results are indicative, and are
applicable to other limestone processing facilities. The aim of the audit was to quantify the
total amount of energy used in the process, and to quantifying and qualifying energy
losses.
The shrinking core reaction model is the most obvious particle reaction model to examine
and is considered to have applicability. The calcination reaction is assumed to initially take
place at the outer surface of the particle, and as the reaction proceeds, the exterior surface
of the particle is covered by the porous product layer, while an unreacted core remains in
the interior region of the particle. The porous layer is assumed to stay intact, giving a
particle of constant size with a shrinking unreacted core.
SHRINKING CORE MODEL
In the shrinking core model there are four important steps which control the rate of
decomposition of calcium carbonate: the conduction of heat through the reacted layer (ash
layer) to the reacting core, the chemical reaction itself at the core, the diffusion of carbon
dioxide away from the core through the porous ash layer, and the diffusion of carbon
dioxide away from the particle through the gas film surrounding the particle.
Film Diffusion Resistance: This refers to the diffusion through the gas film surrounding the
reacting particle which could create a concentration gradient across the film. In most
reactions the resistance to diffusion through the ash layer is usually far greater than
resistance to diffusion through the gas film. The gas film resistance is therefore assumed to
be negligible. Researchers have generally agreed that film diffusion effects are an
insignificant factor in the decomposition of limestone. Film diffusion will therefore be
ignored in this project.
Chemical Reaction Control: This is when the actual reaction at the reacting surface is the
rate determining step.
The rate expression is:
[1]
Solving the equation gives:
[2]
The concentration of solid, CB is equal to its molecular density, B
(3 and 4)
Ash Diffusion Resistance: This is resistance to the flow of gas across the reacted product
and largely depends on the porosity of the product layer. By pseudo steady-state
assumption, the material balance of the reacting component between the centre and the
reaction surface can be written as:
[5]
By differentiating and making the rate of reaction equal to the rate of diffusion:
[6]
Expressing this equation in terms of the reacting fraction of solids:
[7]
This could be expressed as:
(8 and 9)
Particle Internal Heat Transfer Resistance: An alternative to mass transfer resistance by
diffusion is heat transfer resistance by conduction. The ash layer that forms on the outer
region of the particle may act to restrict heat transfer to the reacting core such that the
supply of heat controls the rate of reaction. We have therefore developed an expression
which defines the reaction path when heat transfer is the rate controlling step. This was
done by considering the heat conducted through the ash layer, Qc and the heat absorbed in
the reaction, Qr.
Heat of Reaction (Qr):
The rate of decomposition can be written as:
[10]
This can be written as:
[11]
By substituting for the surface area, S for a spherical particle the rate can be written as:
[12]
The heat flux, or the differential heat flow at the reaction interface can be calculated from
the heat of reaction:
(13]
Substituting the rate expression gives:
[14]
The heat of reaction, Qr for a spherical particle can be obtained by integrating this
expression from radius R to the reaction interface, rc:
[15]
[17]
Heat Balancing:
Under steady state conditions, the heat that is conducted through the ash layer becomes
equal to the heat of reaction. This is the case when heat transfer is the rate determining
step. This means no excess heat is conducted through the ash layer and Qc = Qr
[18]
But the rate, rA can be expressed in terms of reactant or product:
[19]
For the solid product B, the concentration CB is equal to the molecular density B
[20]
Therefore:
[21]
where:
[22]
In developing this model we have assumed that all the heat conducted through the ash
layer is used up in the reaction. This is based on the assumption that the temperature of
the unreacted core homogenises at the reaction temperature, therefore no heating up of
the unreacted core will occur while the reaction progresses. In reality however, Silva et al
[16] found that the temperature of the unreacted core in heat transfer dependent gas-solid
reactions homogenises just below the reaction temperature. However in the case of
limestone, the unreacted core has a very high thermal conductivity, which means the
temperature difference between the unreacted core and the reaction interface is very small.
Therefore only a small amount of heat escapes through the reaction interface to warm up
the unreacted core to the reaction temperature, and we have assumed this to be negligible.
The amount of error introduced by this assumption is therefore very minimal.
The heat conduction controlled model is similar to the ash diffusion controlled model in that
the total reaction time is predicted to be proportional to R2 and to decrease with
temperature. Although investigators generally agree that temperature increases the rate of
decomposition, there is general disagreement on the conditions under which heat transfer
is the rate determining step. The temperature dependency of a reaction is a function of
different parameters: activation energy, pre-exponential factor, the thermal conductivity of
the particle and the temperature dependency of the diffusion coefficient. All these
temperature dependent parameters need to be explored to establish the true temperature
dependency of the reaction. What is presented here is only part of a more detailed study.
EXPERIMENTAL
Limestone (CaCO3) particles were reacted in a preheated oven at seven different
temperatures (850 -1200oC). Five different particle sizes were used (4.75 - 25mm). The
tests were done by heating a 20g sample of each particle size in a preheated oven at the
required temperature. The particles were spread out to minimize inter-particle heat and
mass transfer effects. The mass loss overtime was recorded. The time zero on the reaction
curves represents the time at which the actual reaction started and mass loss started to
occur. The experiment was stopped when no further mass loss was recorded. The Tekumi
limestone, which was used in this experiment, has a purity of 98%. It is a shell material,
with a trigonal crystal structure, and a rhombohedral formation. Impurities include
magnesium carbonate, alumna, silica and iron.
RESULTS
Reaction Rates:
All the experimental data were combined into one reaction curve which was then compared
to the ideal chemical reaction control model and the ash diffusion control model in Figure 2.
Figure 4. The effect of limestone particle radius on total reaction time at temperature Ts =
850oC and assuming Tc = 780oC
The gradient in the plot
(23)
exists for the change in thermal conductivity with temperature, and a log plot of s versus
1/Ts gives a straight line (Figure 5). This would confirm that heat conduction through the
ash layer is rate controlling in the temperature and particle size range studied.
A Lewis number <1 indicates that mass transfer is greater than heat transfer. This means
heat transfer is the rate determining step. When the Lewis Number >1, heat transfer is
greater than mass transfer and the system becomes mass transfer dependent.
Damkohler Number:
The Damkohler number expresses the ratio of chemical reaction kinetics to the rate of mass
transfer. It is the ratio of chemical reaction diffusivity to mass diffusivity.
A Damkohler number <1 indicates that mass transfer is greater than the rate of chemical
reaction. This means chemical reaction kinetics are the rate determining step. When the
Damkohler Number >1, the rate of chemical reaction is greater than the rate of mass
transfer. The system becomes mass transfer dependent.
Chemical-Heat Transfer Number:
In a similar way, a dimensionless number relating thermal diffusivity to chemical diffusivity
has been proposed. It is the ratio of thermal diffusivity to chemical diffusivity, and was
obtained by calculating the ratio of the Lewis Number to the Damkohler Number.
[30]
A NCH number >1 indicates that heat transfer is greater than the rate of chemical reaction,
which means chemical kinetics are rate controlling. When the NCH Number <1, the rate of
chemical reaction is greater than the rate of heat transfer, making the system heat transfer
dependent.
Lime Kinetic Behaviour Diagram
The three dimensionless numbers can be used to construct a "Lime Kinetic Behaviour
Diagram". This was done by evaluating the particle sizes and temperatures at which each of
the dimensionless numbers is equal to one. Figure 6 shows the particle size and
temperatures at which the decomposition of limestone would be chemical reaction, heat or
mass transfer controlled. It is therefore a useful design, troubleshooting and process
improvement tool.
The results show that for >6mm particles, the decomposition of limestone is heat transfer
dependent at temperatures below 1100oC. At these low temperatures, the lower thermal
conductivities and the small internal temperature gradients within the particle would cause
the reaction to be heat transfer dependent. Few authors have reported this kinetic phase.
Hills [14] used thermogravimetric experiments and found the reaction to be heat transfer
dependent, but the results have been discredited by many authors because of the large
samples used in their experiments.
At temperatures above 1100oC the reaction shifts to a mass transfer dependent system.
Under these conditions, the temperature gradient between the surface of the particle and
the reacting core is very high. This, coupled with the higher thermal conductivities, would
cause faster heat transfer through the ash layer. On the other hand, the diffusivity of
carbon dioxide through the ash layer is less temperature sensitive. This means mass
transfer begins to take place at a slower rate than heat transfer. Feng and Lombardo [9]
identified an expansion and shrinking phenomena during calcination. They found that at
900-1100oC CaO expands by 0.2%. This expansion is far less than the tabulated coefficient
of thermal expansion for CaO because sintering and expansion are competing phenomena.
Above 1100oC the particle begins to shrink because sintering becomes predominant
compared to thermal expansion. They reported that intra-particle porosity, number of
pores, total surface area, pore diameter and total porosity all tend to decrease at high
temperatures. These micro-structural changes could be causing a shift from a heat transfer
dependent system to a mass transfer dependent system. Trikkel and Kuusik [17], also
reported pore-blockage above 1100oC, as opposed to high porosity at lower temperatures.
The diffusion of carbon dioxide through the ash layer should become more difficult at high
temperatures, and the reaction becomes mass transfer limited. Adanez, et al [4], also
reported that the specific surface area of calcined limestone is reduced at high
temperatures due to a sintering effect.
The results also showed that the decomposition of lime is chemical reaction controlled for
particles smaller than 4mm. This seems to suggest that a reduction in particle size leads to
a reduction in heat and mass transfer effects within the particle. Work done by Ar and Dogu
[5] fitted the chemical reaction controlled shrinking core model. They used particles as
small as 1.015mm in their gravimetric experiments. Hu and Scaroni [12] also reported that
chemical kinetics were rate controlling for particles smaller than 10m. Borgwardt, [6],
found the decomposition to be 'reaction rate controlled' for very small particles (1-90m).
However the results obtained by Acke and Panas [3] could not fit this model, even though
they used the same particle size range. This difference could be attributed to the bigger
sample weights used in their experiments. Inter-particle heat and mass transfer could have
affected their results.
For 4-6mm particles, the results show that the reaction shifts between chemical kinetics
and heat and mass transfer kinetics. These intermediate particles are large enough to
experience some heat or mass transfer effects, but small enough to be chemical kinetics
dependent. Garcia-Labiano et al [10], reported that the reaction shifts between chemical
kinetics and mass transfer for 90m-6mm particles. Thermogravimetric analysis work done
by Khinast et al, [14] suggested that the rate determining step shifts between chemical
kinetics and mass transfer, depending on particle size and CO2 partial pressure. Hu and
Scaroni [12] did some scanning electron microscopic analysis work and concluded that
chemical kinetics, heat transfer and mass transfer all offered resistance to the calcination
by fitting a set of lifters in the kiln. Although both systems increased the mixing and
turbulence in the kiln, the trefoil increased the heat transfer surface area by 180%, hence
the additional energy efficiency improvement. This is despite the fact that the trefoil acts as
an airflow shield, thereby increasing both carbon dioxide concentration and furnace
pressure.
Industrial Application of the Trefoil
The results were transferred to an industrial kiln. A 4m long trefoil section was placed just
before the beginning of the calcination zone. The positioning of the trefoil extended the
calcination zone and increased heat transfer.