Chemical Engineering Science 60 (2005) 4609 4622

www.elsevier.com/locate/ces

Modelling of a rotary kiln for the pyrolysis of aluminium waste

F. Mariasa, , H. Roustanb , A. Pichatb
a Laboratoire Thermique Energtique et Procds (EA 1932), ENSGTI, Rue Jules Ferry, B.P. 7511, 64075 Pau Cedex, France
b Centre de Recherches de Voreppe Pechiney, 725, rue Aristide Bergs, BP 27, 38341 Voreppe, Cedex, France

Received 14 September 2004; received in revised form 8 March 2005; accepted 14 March 2005
Available online 17 May 2005

Abstract
This paper deals with the mathematical modelling of a rotary kiln, which is used for the recycling of aluminium waste. This model is
mainly based on the coupling between

a bed model describing the processes occurring within the bed of aluminium waste owing inside the kiln,
a kiln model describing heat transfer within the kiln itself,
a gas model describing processes occurring within the gaseous phase held inside the furnace.
The bed model is mainly based on the plug ow of particles of aluminium inside the kiln. Mass balances as well as energy balances
allow for the prediction of the fraction of the organic material within the particles of aluminium as well their temperature. Relevant
equations for the kiln model include heat conduction and heat exchange with solid and gaseous materials. The equations for the gas
model are mainly based on uid mechanics equations coupled with turbulence, radiation, and combustion. The software Fluent will
be used in order to solve this last model. In this paper, some insight will be given on the description of the bed model and the kiln
model and on the procedure used for the coupling of these models. Exchange variables as well as solving procedure will also be included.
Numerical results will be compared to experimental ones, obtained from the pilot scale rotary kiln at Pechineys research centre.
2005 Elsevier Ltd. All rights reserved.

Keywords: Rotary kiln; Pyrolysis; Aluminium; Modelling; Waste

1. Introduction Fig. 1 sketches the experimental device under consider-

The goal of this study is to construct a mathematical model
able to predict the physico-chemical processes occurring
when particles of aluminium coated with organic materials
(polish in the case of cans, cardboard in the case of milk
packaging, etc.) are introduced into a rotary kiln in order to
be cleared of their organic content. This model, once vali-
dated upon experimental tests on a pilot scale, will be used
in order to enhance the operating parameters of industrial
units owned by Pechnineys group.
Corresponding author. Tel.: +33 559 407 809;
fax: +33 559 407 801.
E-mail address: frederic.marias@univ-pau.fr (F. Marias).
0009-2509/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.03.025
ation (rotary kiln operating at counter current conditions).
The goal of the study is to predict
the composition of the particles of aluminium leaving the
furnace (in terms of organic content, for example),
their temperature at the kiln exit,
the state of the aluminium (in terms of oxidation),
the composition of the exhaust gas (mass fraction of hy-
drogen, methane, carbon monoxide, etc.).
This prediction requires a geometrical description of the de-
vice (diameter, length, inclination, etc.) as well as operat-
ing parameters (the mass ow rate of aluminium, electrical
power on the heating furnaces, etc.).
Before entering the section devoted to the formulation of
the mathematical model, it is necessary to check the relevant
4610 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622
Particles
Aluminium
Rotary kiln
Pelec
Pelec
Gas
Alu.
Electrical heaters
Fig. 1. Sketch of the device under consideration.
processes occurring within the furnace. These phenomena
can be described by tracking a particles path from its supply
to the kiln to its exit (Boateng and Barr, 1996a,b; Chen et
al., 1993; Chen and Lee, 1994; Heydenrych et al., 2002;
Leger et al., 1993d; Li et al., 1999a,b; Martins et al., 2001;
Marias, 2003; Patisson et al., 2000; Sudah et al., 2002):
transport of the particle under the rotation and inclination
of the kiln,
heating of the particle (radiation, heat transfer inside and
outside of the particle, etc.),
decomposition of organic material (pyrolysis),
diffusion of volatiles outside the particle,
potential oxidation of aluminium.
From the gaseous side of the process, the relevant phe-
nomena are turbulent ow with chemical reaction and radia-
tion (Jackway et al., 1996; Leger et al., 1993ac; Mastorakos
et al., 1999):
turbulence,
chemical oxidation of the products of pyrolysis,
interaction between turbulence and combustion,
heat transfer (convection and radiation).
Finally, conduction inside the kiln, heat exchange between
the kiln and the bed of solids as well as heat exchange
between the kiln and the gaseous material are important
phenomena.
The whole system is thus highly complex and heteroge-
neous. Nevertheless, one can consider that it is composed of
three different parts (the bed of solid material, the kiln, the
gaseous material), which exchange both mass and energy.
The following part of this paper will focus on the descrip-
tion of the hypothesis we have used in order to construct a
mathematical model of this system.
2. Mathematical modelling
2.1. The kiln
The kiln plays a major role in the total amount of heat
transferred within the furnace. Indeed, it receives the ther-
Pelec

gas,kiln
Air

bed

elec

ext
Fig. 2. Sketch of specic heat uxes to the kiln.
mal power released by the heating furnaces and releases it
towards the bed of solid particles of aluminium to be repro-
cessed. That is why, for our modelling purposes, the measure
of its temperature is required.
2.1.1. Hypothesis
The kiln is supposed to be a cylinder of stainless steel of
inner diameter D, of length L and of thickness e. It is fully
three dimensional. It undergoes several heat uxes, and their
total amount results in its thermal equilibrium. The specic
heat uxes are (Fig. 2) as follows:

ext the heat exchange with surrounding air,

elec the heat exchange with heating furnaces (electrical
power dissipated into heat),

gas,kiln the heat exchange with the gas held within the
furnace,

bed the heat exchange with the bed of aluminium parti-
cles to be reprocessed.
Finally, because of radial and axial temperature gradients
within the kiln itself, conduction inside the kiln must be
taken into account.
In polar coordinates both temperature and heat uxes de-
pend on r,  and z (r being held in the range of [D/2
D/2 + e]).
Patisson et al. (2000) have shown that the dependence on
 is very important since it is a direct result of the position
of the bed of solid particles within the kiln. (The load is
not evenly distributed over the circumference of the kiln.)
Nevertheless, in order to reduce the complexity of the overall
model, this dependence has been lumped, and the choice
has been made to compute an average temperature over the
circumference of the kiln. Moreover, because of the measure
of the thickness of the kiln and because of the order of
magnitude of the thermal exchange coefcient, the low value
of Biots number (Bi = he/ e) has led us to consider the
 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622
1 1
gext (-)
Heater 1 Heater 2
0 0
0 L
Fig. 3. Shape of the function gext (z).
kiln as being a thin material. The rst hypothesis is then the
following:
H1. The temperature of the kiln solely depends on the axial
position: Tkiln = Tkiln (z).
The second hypothesis is linked to the thermal power
released by the electrical furnaces:
H2. It is supposed that the total amount of electrical power
received by the heaters is completely released as heat
power and that this heat is completely and evenly dis-
tributed over the circumference of the kiln.
The last hypothesis deals with the thermal conductivity
of the kiln, which is supposed to be constant:
H3. The thermal conductivity of the kiln is constant (kiln ).
2.1.2. Mathematical modelling
Specic heat uxes: It is supposed that the heat exchange
with the surrounding air is of the convective type. Thus, this
exchange is computed by

ext = gext (z)hext (Tkiln (z) T ), (2.1)
where gext is a threshold function (Fig. 3) taking into account
the geometry of the system, hext is the external heat transfer
coefcient (20 W m2 K 1 , Taine and Petit (1989)) and T
is the room temperature (25 C).
Taking into account hypothesis H2, one is able to write
the heat ux received by the furnace from the heaters as


1 g1 (z)P1 g2 (z)P2

elec (z) = + , (2.2)
D Lheater1 Lheater2
where g1 and g2 stand for geometrical functions (Fig. 4), P1
and P2 are the thermal powers released by the heaters and
Lheater1 and Lheater2 their respective lengths.
4611
g1 (-) g2 (-)
Heater 1 Heater 2
0 L
Fig. 4. Shape of the functions g1 (z) and g2 (z).
The mathematical expression of heat transfer between the
kiln and the gaseous material will be given in the section
devoted to the modelling of radiation inside the furnace.
Because of the low velocity of the particles of solid in-
side the furnace, we suppose that heat transfer between the
moving bed and the kiln is mainly conductive and radiative.
Following the work of Patisson et al. (2000), we have ex-
pressed the heat ux as follows:
bed

bed (z) = hbed (Tbed (z) Tkiln (z)) , (2.3)

where hbed =25 W m2 K 1 is the heat exchange coefcient
between the kiln and the bed of solids and bed is the angle
of overlap of the bed inside the kiln (see the paragraph
devoted to the modelling of solid particles). The value of
the heat transfer coefcient has been adjusted in order to t
the experimental data more precisely to reach the ambient
temperature for the bed of solids at the exhaust of the kiln.
Energy balance: Let us consider an annulus of length dz
of the kiln. If Fouriers law is assumed for the description
of conduction, the energy balance leads to
kiln ej2 Tkiln /jz2 =
elec +
exter
gas,kiln +
bed .
(2.4)
The solving of this equation requires:
the temperature of the bed Tbed ,
the heat ux from the gas to the kiln
gas,kiln .
2.2. The bed of solids
Before entering the section devoted to the modelling of
this part of the system, it is necessary to describe the par-
ticles that form the bed. That is why, rst of all, we will
focus on the description of the particles of aluminium to
be reprocessed. This description will cover both physical
4612 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622

comprises the coating of the particle, we assume the follow-

S0
ing to be true:
eorg,0
Particles are supposed to be dry at the feed of the furnace.
eAl,0
The organic material is solely composed of carbon, hy-
drogen and oxygen.
The volatile material released by pyrolysis is a mixture of
Fig. 5. Sketch of the particles to be reprocessed. hydrogen, methane carbon monoxide and carbon dioxide.
Fixed carbon held within the organic material is released
(size, shape factor, etc.) and chemical (composition, kinetics as volatiles. No heterogeneous reaction will be taken into
for pyrolysis reaction) analyses. account.

Thus, in order to fully describe the organic material, the

2.2.1. Particles
following data are required:
Geometrical characterisation: By their nature, the parti-
cles can be considered to be a basis of aluminium covered
Ultimate analysis (C% , H% , O% , on a weight basis).
with one or several organic materials. Generally, their shape
Proximate analysis (volatiles, xed carbon and ashes con-
factor  is much lower than one. For our modelling pur- vol , y Cx , y ash .
tent, on a weight basis), yorg,0 org,0 org,0
poses, they will be considered as a stack of two materials
The lower heating value of the material: LHVorg .
sharing a surface S0 (Fig. 5).
Heat of the pyrolysis reaction:r horg,pyro .
In order to simplify the mathematical formulation of the
Reaction kinetics: the order of reaction (n) activation en-
problem the following assumptions have been used:
ergy, (Ea ), pre-exponential factor (A). Indeed, it is sup-
posed that the reaction rate is of the form (Bockhorn
the surface of the particle is not modied as it passes
et al., 1996):
through the furnace S = S0 ,


aluminium is neither consumed nor oxidised in the fur- d Ea
nace. Thus, its thickness remains constant: eAl = eAl,0 , = A exp (1 )n , (2.10)
dt RT
the organic material coating the particle to be reprocessed
is progressively consumed inside the furnace. Its thickness morg,0 morg
= . (2.11)
is variable (eorg ). morg,0 morg,

Given these assumptions, one can consider that:

Finally, we write
The total thickness of a particle is the sum of the thickness eorg = eorg,0 (yorg,0
vol Cx
+ yorg,0 )(1 ) + eorg,0 yorg,0
ash
, (2.12)
of the organic material and of the aluminium:
where  increases from 0 to 1 within the furnace.
epart = eAl + eorg = eAl,0 + eorg . (2.5) The composition of the volatiles is determined by the
The shape factor of a particle is computed by atomic and energy balances (Marias, 1999):

  1/3
1/3 MC vol MC vol MC vol

 C% = z + z + z , (2.13)
 = (6epart )2/3 = (6epart )2/3 . (2.6) MCH4 CH4 MCO CO MCO2 CO2
S S0
2MH vol 4MH vol
Its density is given by H% = zH2 + z , (2.14)
MH2 MCH4 CH4
Al eAl + org eorg Al eAl,0 + org eorg
part = = , (2.7) PCIorg = PCIH2 zH
vol
+ PCICH4 zCH
vol
+ PCICO zCO
vol
, (2.15)
eAl + eorg eAl,0 + eorg 2 4

where Al and org stand respectively, for the intrinsic zH

vol
2
+ zCH
vol
4
+ zCO
vol
+ zCO
vol
2
= 1. (2.16)
densities of aluminium and of the organic coating.
The composition (on the weight basis) of a particle is This composition is supposed to be constant along the axis
of the furnace.
Al eAl Al eAl,0 To conclude with the description of solid particles, it is
YAl = = (2.8)
Al eAl + org eorg Al eAl,0 + org eorg necessary to associate a model for total enthalpy. If a particle
is supposed to be equivalent to aluminium, volatiles and
Yorg = 1 YAl . (2.9)
ashes, then its enthalpy is written as follows:


mvol mash
Chemical characterisation: Before entering the sec- hpart = YAl hAl + Yorg hvol + hash , (2.17)
tion devoted to the pyrolysis of the organic material that morg morg
 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622 4613

R
bed

Hbed
bed
kiln
lbed

Fig. 6. Geometrical data of the furnace.

hAl = cp,Al (Tpart Tref ), (2.18) at a constant speed. This is computed as the ratio of the

 Tpart  length of the kiln to the mean residence time of a parti-
hvol = zH2 hf,H2 +
vol 0
cp,H2 (T ) dT cle inside the furnace: ubed = L/. This residence time is
Tref computed according to Li et al. (2002b):

 Tpart 
+ zCH4 hf,CH4 +
vol 0
cp,CH4 (T ) dT L sin bed
Tref = . (2.21)

 Tpart  2Rnrot (tan kiln + cos bed tan )cos2
+ zCOvol
h0f,CO + cp,CO (T ) dT Finally, the porosity of the bed is assumed to be constant
Tref

 Tpart  within the whole furnace ( = 0.5).
+ zCOvol
h 0
+ c p,CO2 (T ) dT , (2.19) Mathematical modelling: As of now, N will stand for the
2 f,CO2
Tref lineic concentration of particles within the kiln. If we as-
hash = cp,ash (Tpart Tref ). (2.20) sume that these particles are neither subject to attrition nor
to agglomeration, the concentration is constant inside the
2.2.2. The bed of solids furnace. Thus, in steady state
The previous paragraph has given insight into the descrip- dN
tion of one particle. Nevertheless, in the kiln, particles are = 0. (2.22)
dz
fed continuously. Thus, they are in the shape of a bed of
solids inside the furnace. The next paragraph is devoted to At the feed of the kiln, the number of particles must match
the description of this bed. the total mass ow rate to be processed. Thus, if Qw and
Assumptions: Several studies have focused on the mod- ubed respectively, denote this ow rate and the velocity of
elling of the motion of solid particles inside a rotary kiln. the bed, we write as follows:
(Boateng and Barr, 1996a,b; Boateng and Barr, 1997; Henein Qw
et al., 1983a,b; Heydenrych et al., 2002; Li et al., 2002a,b). N0 = . (2.23)
pat,0 S0 epart,0 ubed
Most detailed models describe the bed of solids as a pseudo-
tri-dimensional media. In the framework of this study, and Given the value of  (2.11), we are able to compute the
in order to simplify the mathematical description of the sys- specic mass ow rate of volatiles released from the bed
tem, and in accordance with several researchers (Chen and and received by the gaseous phase:
Lee, 1994; Patisson et al., 2000), the bed is supposed to be

N Ea
in plug ow inside the kiln. mpyro = org eorg,0 S0 (yorg,0 1)A exp
ash

Given some of the geometrical data of the kiln and llit RT part
n
its lling rate, one can compute the ratio (Hbed /R) (1 ) . (2.24)
(see Fig. 6) and Froudes number of the furnace (for con- If Sbed stands for the cross-sectional area of the bed, the
dentiality reasons, the geometrical data are not further mass balance over a slice of thickness dz of the kiln leads to
detailed):
dSbed part
Hbed
2 R (1 )ubed = lbed m pyro (2.25)
0.3 and F r = 1 103 . dz
R g
and the energy balance leads to
Thus, in accordance with the work of Henien et al.
dSbed part hpart
(1983a,b) we consider that the kiln operates under the (1 )ubed = lbed (m pyro (hvol + r horg,pyro )
rolling mode. dz
Finally, we suppose that the bed of solids proceeds +
gas,bed )
bed D,
through the kiln (under its motion of rotation and its slope) (2.26)
4614 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622

where
gas,bed stands for the heat ux released by the gas to Then we compute the specic heat uxes released by the
the bed. Further details about the computation of its value gas to the bed of solids and to the kiln:
will be given later. bed
Finally, geometrical considerations lead to
uent
gas,bed = (4 Tbed
4
Gbed ), (2.32)
2(2 bed )
 
lbed = D sin
bed kiln
, (2.27)
uent
gas,kiln = (4 Tkiln
4
Gkiln ), (2.33)
2 2(2 kiln )
8Sbed where bed and kiln stand, respectively, for the emissivities
bed sin bed = , (2.28)
D2 of the bed and the kiln (assumed to be equal to one as of
now).
N S 0 epart These heat uxes being fully three dimensional, it is nec-
Sbed = . (2.29)
1 essary to sum up these uxes over the lling angle in order
to make them one dimensional (as is required by the bed
2.3. Gas held within the furnace model):
 bed
Several researchers have shown that computational uid
gas,bed =
uent
gas,bed d, (2.34)
dynamics is well suited for the description of processes oc- 0
curring within the gaseous phase of a rotary kiln (Jackway et  2bed
al., 1996; Leger et al., 1993ac; Marias, 2003; Mastorakos
gas,kiln =
uent
gas,kiln d. (2.35)
et al., 1999). Thus, in the frame of this study, the commer- 0
cial software Fluent is used for this specic aspect. The Because the radiation between the exposed wall and the bed
governing equations of this software will not be developed operates trough the gas held in the furnace, this mode of
here. The interested reader should refer to the Fluent Users radiative heat transfer is taken into account, by essence, by
guide. The following models have been used: the discrete ordinates model.

Turbulence: k  model.
Chemistry of the system: chemical equilibrium computed 3. Solving
by minimisation of Gibbs free energy (7 species are taken
into account: CH4 , H2 , CO, CO2 , H2 O, O2 , N2 ). The previous paragraphs have given the equations for
Interaction turbulence-combustion: density probability the mathematical representation of the processes occurring
function (pdf). within the bed, the kiln and the gas phase. The coupling be-
Radiation: discrete ordinates model (discretisation  = tween these parts is highly important. According to previous
5,
= 5). work (Marias, 2003), we have chosen to separately solve the
part relative to the gaseous phase and the part corresponding
Dealing with radiation, the discrete ordinates model al- to the bed of solids and the kiln. The rst program requires
lows for the computation of the radiation intensity at every the specic mass ow rate of volatiles released by the bed,
location of the gaseous phase (Raithby and Chui, 1990): m pyro , and its temperature, Tbed , as well as the kiln temper-
ature, Tkiln . On the other hand, the program which describes
.(I (r , s)s ) + (a + s )I (r , s) the processes occurring within the kiln and bed requires the

T 4 s 4 knowledge of the specic heat uxes they receive (
gas,bed
= an2 + I (r , s )(s .s ) d . (2.30)
 4 0 and
gas,kiln ).
In this paragraph, we focus on:
This model has been used because it is available in the Fluent
Package (Monte Carlo approach model is not) and because Variables and equations solved by the program kiln-bed.
it allows for computation in combustion problems (the ab- The numerical procedure for the solving of the overall
sorption coefcient is a function of the local concentration model (exchange variables and general algorithms).
of species such as CO2 and H2 O), and also because its com-
putational cost is moderate and its memory requirements are 3.1. The program kiln-bed
modest.
From knowledge of the radiation intensity I, in every di- Here, we remind the reader of the computed variables and
rection (it depends on the discretisation) one is able to com- their associated equations.
pute the incident radiation on a wall:
 4  rate of progress of pyrolysis (Eq. (2.11)).
Gw =
Iw (r , s ) d .
(2.31) epart thickness of a particle to be reprocessed (Eq. (2.5)).
0 part density of a particle (Eq. (2.7)).
 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622 4615

gas,kiln
Gas

Tkiln

gas,bed
Kiln
.
m''pyro
Tbed

bed

Bed

Fig. 7. Sketch of the numerical exchanges between the different models.

m pyro specic mass ow rate of volatiles released by the

bed (Eq. (2.24)). Initialisation
lbed width of the bed (Eq. (2.27)).
0kiln,bed
0gas,bed
bed lling angle of the furnace (Eq. (2.28)).
Sbed area of the cross-sectional area of the bed
(Eq. (2.29)). Solving
N lineic concentration of particles (Eq. (2.22)). MatlabTM "kiln-bed"
.
hpart enthalpy to weight of a particle (Eq. (2.26)). m"pyro Tkiln Tbed
Tpart temperature of a particle (Eq. (2.17)).

exter specic heat ux lost by the kiln to the surroundings
(Eq. (2.1)).
Conversion

elec specic heat ux received by the kiln from electrical MatlabTM . . fluent
heaters (Eq. (2.2)). m"pyro m"pyro

bed specic heat ux received by the bed from the kiln
(Eq. (2.3)).
Tkiln temperature of the kiln. (Remark: to keep the overall Solving
system of the rst-order type, we introduce the following FluentTM "Gas"
ju
variable: u = dTkiln /dz; it is the solution of kiln e jz = fluent
fluent

gas,bed gas,kiln

elec +
exter
gas,kiln +
bed .)

The overall system is a differential algebraic system. It is Conversion
composed of 17 equations, ve being differential of the rst MatlabTM
gas,bed
fluent

gas,bed
order. The associated boundary conditions are:
gas,kiln
fluent
gas,kiln

Tpart (z = 0) = T0 ,
N(z = 0) = N0 (see Eq. (2.23)),
epart (z = 0) = epart,0 ,
Yes
kiln u(z = 0) = hext (Tkiln (z = 0) T ) + hbed (Tbed (z = Convergence
0) Tkiln (z = 0)),
kiln u(z = L) = hext (Tkiln (z = L) T ) + hbed (Tbed (z =
L) Tkiln (z = L)).
No
Thus, the system is of a boundary type. Nevertheless, End
because of the differential algebraic equations and the stiff
nature of the system, the choice has been made to use an Fig. 8. Solving procedure.
integrator of the predictorcorrector type (Gears method).
Since this type of solver is of the initial value type, it is
necessary to include this integrator into a general iterative
program. More precisely, at each step of the iterative method,
the value of the temperature of the kiln at z = 0 is supposed. the kiln at z=0 is assumed. This iterative process is run until
Then the kiln-bed model is run and we are able to check if convergence is reached (the boundary condition at z = L is
the boundary condition at z = L is satised. If it is, then the satised).
solution is accepted, if it is not then another temperature of This program is solved using the software Matlab.
4616 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622

3.2. Solving of the overall model Table 1

Characteristics of particles in question
Fig. 7 shows the interactions between the different parts Can covers
of the model as well as the exchange variables. The solv-
Geometrical
ing of the overall model is iterative, the iterative criterions
S0 (m2 ) 104
being m pyro ,
gas,bed and
kiln,bed . Fig. 8 shows the solving epart,0 (m) 106.106
procedure.
The convergence is checked by the evolution of the ex-
Composition (raw)
change variables (m pyro ,
gas,bed and
kiln,bed ) between it- YAl,0 (dimensionless) 0.985
erations. A Java software has been constructed in order to Yorg,0 (dimensionless) 0.015
automate the iterations and the intervention of each program.
Organic material
ycend,0 (dimensionless) 0.172
C% (dimensionless) 52.94
4. Results and confrontation with experiments H% (dimensionless) 7.84
O% (dimensionless) 39.22
The centre de recherche Pechiney de Voreppe (CRV) owns LHV (MJ kg1 ) 22
a rotary kiln at pilot plant scale. Unfortunately, for reasons
of condentiality, we are neither able to provide information Pyrolysis data
about the characteristic length and diameter of the kiln, nor A (mn1 ) 1.35.1014
the electrical powers sent to the heating furnaces. These Ea (J mol1 ) 195000
n (dimensionless) 2
powers are controlled by regulators that ensure a temperature
of 250 C at the centre of the rst electrical heater and a
temperature of 570 C at the centre of the second one. The
comparisons between experiments and model predictions 600
will be presented in a dimensionless form without the Final temp.
particles to be reprocessed (cold experiment) and with the
particles (full experiment) (Fig. 9).
400
4.1. Characteristics of particles Iterations
Tkiln(C)

The particles in question are covers of cans. The most

relevant data are provided in Table 1. Dealing with pyroly-
200
sis, results are issued from an ATG analysis of the organic

1
0
Exp. 0 L /2 z L
0.8 Model
Fig. 10. Sketch illustrating convergence in the case of the cold
experiment.

0.6
material under study. More precisely, the method is based

(-)

on the minimisation of the difference between experimental

0.4 data and values computed by the pyrolysis model (Bockhorn
et al., 1996).

0.2 4.1.1. Cold experiment

The mass ow rate of air supplied to the furnace corre-
sponds to the one used in the case of can covers. The thermal
0
200 400 600 800
powers yielded by the electrical heaters are P1 =0.9% P1,max
T (K) and P2 = 1.3% P2,max . The convergence of the model is en-
sured by the non-evolution of the exchange data after 20 it-
Fig. 9. Comparison between experimental data and model of pyrolysis of erations (a relaxation factor of 0.1 has been used to stabilise
the organic material coating aluminium particles. the solving procedure). Fig. 10 shows the convergence path.
 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622 4617

600 of the furnace corresponding to space between the two

Experiment heaters. Indeed, we have assumed, in the model, that this
Model region underwent exchange with ambient air at 25 C. How-
ever, precisely because the heaters are not perfect, some of
the heat they released is lost to the surrounding air, leading
400 to an increase in the local temperature of the ambient air.
Taxis (C)

4.1.2. Hot experiment

200
0
0 L /2
Fig. 11. Temperature in the axis of the kiln. Comparison experiment
versus model (Cold experiment).
Fig. 11 shows the evolution of the temperature on the
axis of the kiln, from both experimental and numerical data.
The agreement between the two sets of data is quite good.
The value of the maximal temperature on the second heater
predicted by the model is a little bit smaller compared to
the experimental value. A small increase in the electrical
power sent to the second heater should correct this slight
discrepancy. There is also a slight difference in the zone
For reasons of condentiality, we are neither able to give
the mass ow rate of waste nor the mass ow rate of the air
used in this experiment. The equivalence ratio has been set
at 0.18 (lean conditions). Two numerical experiments have
been performed. In the rst one, the combustion of volatile
matter released by the pyrolysis of organics takes place. The
electrical powers have been tuned to t the experimental
z L data (in terms of temperatures at the centre of electrical
heaters). Finally, the following values have been kept: P1 =
0.5% P1,max and P2 =2% P2,max . In the second experiment,
the combustion has been switched off in order to measure
the importance of the oxidation of volatiles in the energy
balance and to compare to experimental data (indeed, in
the experimental procedure, a decrease in the power sent
to the second heater is measured once combustion begins).
Once again the electrical powers have been tuned so that
the value of the temperature at the centre of each heater
equals the set point of the controllers (respectively, 250 C
for the rst heater and 570 C for the second heater). The
following values have been kept: P1 =2.7% P1,max and P2 =
3.1% P2,max (Fig. 12).

12
600
m"pyro 10-4 (ks.m-2.s-1)

Final flux Final temp.

8
Tkiln (C)

400

4
200
.
0
0
0 1 2 0 1 2
z (m) z (m)

4000
600
2000 Final temp.

gas,bed (W. m-2)

0 400
Tbed (C)

-2000
200
Final flux
-4000

-6000 0
0 1 2 0 1 2
z (m) z (m)

Fig. 12. Sketch illustrating the convergence in the case of the load of can covers.
4618 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622
600
Experiment
Model (no comb.)
Model (comb.)
400
Taxis (C)
200
0
0 L /2 z L
Fig. 13. Comparison experiment (Cold experiment) versus model (Hot
experiment with and without combustion).
In order to compare the results of the model with
experimental data, we have once again used the prole of
temperature along the axis of the kiln. Nevertheless, the
experimental prole has not been recaptured during the
hot experiment. That is why we use the cold prole. We
expect this prole to be sufciently relevant because of the
mode of operation of controllers. At least, we can compare
with the value at the centre of the electrical heaters.
Fig. 13 shows accurate correlation between numerical pre-
diction and experimental data in the case where combus-
tion is switched off. The higher value of the temperature
in the zone corresponding to the position of the rst heater
Fig. 14. Predicted prole of temperature (K) inside the furnace (Hot experiment with combustion).
( 20 C) is linked to the overly high value of the electrical
power sent to the rst heater.
In the case of the prediction with oxidation of the volatiles,
the prole of temperature is in quite good agreement in the
vicinity of the second heater. It is quite different near the
rst heater. More precisely, Fig. 13 shows a temperature
peak downstream of the heater. As it will be shown in the
following paragraphs, this peak is linked to the position of
the region where the oxidation of the volatiles takes place.
Indeed, because of the counter-current mode of operation
of the system, the volatiles released near the second heater
are recirculated towards the input of the kiln and are burned
upstream. It is also noteworthy that the value of the temper-
ature at the centre of the rst heater (z L/4) is equal to
the value of the set point of the controller ( 250 C).
Figs. 14, 15 and 16, respectively, represent the elds of
temperature as well as the mass fraction of O2 and CO2 in-
side the furnace. Transversal slices are located at the kiln
input, (from the particles point of view) at the centre of the
rst electrical heater, at the centre of the second electrical
heater and at the output of the kiln. The rst information
they yield is relative to the location where volatile oxida-
tion takes place. Indeed, it is clearly located between the
two heaters, where temperature reaches its maximal value
( 600 C) and where there is a sharp decrease in the oxy-
gen mass fraction.
Fig. 17 yields further insight into this analysis. More pre-
cisely, it shows that the pyrolysis of the coating is located
within a very narrow band within the second heater. Analy-
sis of Fig. 18 coupled with Fig. 17 shows that we can expect
450 C to be the value for the ignition of pyrolysis. We can
also see that temperature proles of the kiln and the bed are
quite equivalent, demonstrating that heat transfer between
 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622 4619

Fig. 15. Predicted prole of mass fraction of O2 dimensionless inside the furnace (Hot experiment with combustion).

Fig. 16. Predicted prole of mass fraction of CO2 dimensionless inside the furnace (Hot experiment with combustion).

1 1

0.8
m''pyro (kg.m-2.s-1) 103

Al.
0.6 Vol. coat. 0.6
Y (-)

Coating.
Ash coat. 0.4

0.2 0.2

0 0
0 L /2 z L 0 L/2 z L

Fig. 17. Predicted prole of specic mass ow rate of volatiles released from the bed to the gas and composition of particles in terms of aluminium,
coating mass fraction, volatiles and ash mass fraction within the coating (Hot experiment with combustion).
4620 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622
600
Tkiln
Tbed
400
T (C)
200
0 -7000
0 L /2
Fig. 18. Predicted prole of temperature of the bed of solids and of the kiln; specic heat uxes inside the kiln (Hot experiment with combustion).
them is quite efcient. Finally, Fig. 18 illustrates heat trans-
fer within the kiln. We can see that in the vicinity of the rst
heater, the gas yields energy to the bed of solids, which in
turn yields energy to the kiln. We can also see the location
of the electrical heaters. Finally, we can see that downstream
of the kiln, a great amount of heat is transferred from the
bed to the gas, leading to the cooling of the bed by fresh air
entering counter currently.
Experimental results show a decrease in the electrical
power sent to the second heater of approximately 65% when
the combustion of volatiles begins (it goes from a 15% maxi-
mal value to 10%). This corresponds perfectly to the numer-
ical prediction. Indeed the power sent to the second heater
goes from 3.1% to 2%, which is the same ratio as in the ex-
perimental data. Dealing with gas analysis at the exit (from
the gas side) of the furnace, experimental results are as fol-
lows:
%vol CO2 [10 14]
%vol O2 [7 11].
The average values computed by the model give 10% for O2
and 10% for CO2 , which also correspond perfectly.
5. Conclusion
A complete mathematical model for the pyrolysis of
coated waste of aluminium has been developed. It is based
on a coupling between two sub-models representing
the bed of solids to be reprocessed and the kiln itself, and
the gaseous phase where the volatiles are released (as a
result of pyrolysis) and where their oxidation takes place.
The rst of these sub-models considers the bed of solids
as a plug ow reactor where pyrolysis occurs. It takes into
account heat transfer by conduction in the kiln as well as
heat transfer with the surroundings (both ambient air and
electrical heaters) and with the kiln. The second of these
sub-models deals with processes occurring within a gaseous
media where turbulent combustion occurs. Chemistry, turbu-
lence and radiation have been taken into account. Equations
3000
1000
0

(W.m-2)
-1000

exter

bed -3000

elec

gas,kiln -5000

gas,bad
z L 0 L /2 z L
of this sub-model are solved using the commercial software
Fluent.
A global iterative procedure allows for the exchange of
relevant data (specic heat uxes from gas to bed and kiln,
the specic mass ow rate of volatiles) until convergence of
the whole model is reached.
Comparisons with experimental investigation have been
performed in the case of particles of covers of cans. They
are congruous, at least qualitatively. Nevertheless, operating
parameters must be known much more precisely in order to
carry out quantitative analysis. Indeed, it would be better if
we could compare the prole of temperature in the case of
the hot experiment as well as the prole of species inside
the furnace.
Anyway, some conclusions can already be drawn from
the analysis of the results yielded by the model. Indeed, the
value of 450 C seems to be the ignition value for which
pyrolysis begins to occur (for the particular coating in ques-
tion). Moreover, because of the oxidation of the volatiles and
because of the mode of operation of the furnace (counter-
current) a high amount of the heat released by combustion
is received by the bed in the vicinity of the rst heater. This
would indicate that perhaps there is no need to preheat the
aluminium to be reprocessed (if the heating rate of a particle
is the same). Moreover, because of the value of the ignition
temperature, there is probably no need to set the temperature
inside the second heater to 570 C.
These kinds of conclusions could diminish the cost (from
an energy-saving point of view) of the operation of repro-
cessing. Moreover, they could help diminish the level of
temperature reached inside the furnace and then diminish
the risk of the oxidation of aluminium.
Notation
A pre-exponential factor for pyrolysis data,
mn1
D inner diameter of the kiln, m
e thickness of the kiln, m
eAl width of aluminium on a particle to be repro-
cessed, m
 F. Marias et al. / Chemical Engineering Science 60 (2005) 4609 4622 4621

eorg width of organic material (coating) on a par-  porosity of the bed of solids, dimensionless
ticle to be reprocessed, m kiln thermal conductivity of the kiln, W m1 K 1
epart width of a particle, m Al intrinsic density of aluminium, kg m3
Ea activation energy of pyrolysis reaction, org intrinsic density of organic coating, kg m3
J mol1 part density of a particle to reprocess, kg m3
hAl enthalpy to weight of aluminium held within  mean residence time of particles inside the
a particle, J kg1 furnace, s
hext external heat transfer coefcient, W m2 K 1
bed specic heat ux from the kiln to the bed,
hbed heat transfer coefcient between bed of solids W m2
and kiln, W m2 K 1
elec specic heat ux received by the bed from
hpart enthalpy to weight of a particle to be repro- electrical heaters, W m2
cessed, J kg1
ext specic heat ux lost to the surroundings,
hvol enthalpy to weight of volatiles held within a W m2
particle, J kg1
gas,bed specic heat ux from the gas to the bed,
Hbed height of the bed of solids inside the bed, m W m2
lbed width of the bed of solids, m
gas,kiln specic heat ux from the gas to the kiln,
L length of the kiln, m W m2
Lrechauf k length of electrical heater k, m  shape factor of a particle, dimensionless
LHVorg lower heating value of the organic coating,
angular velocity of the kiln, rad s1
J kg1
morg mass of organic material (coating) inside a
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