JOURNALol

ANALYTlCALnd
APPLIED
PYROLYSIS
Journal of Analytical and Applied Pyrolysis
ELSEVIER 30 (1994) 101-120

Kinetic model of the pyrolysis of polyethylene in a

fluidized bed reactor
Juan A. Conesa *, Antonio Marcilla, Rafael Font
Departmeni of Chemical Engineering, University of Alicante, Apartado 99, Alicante, Spain

Received 29 March 1994; accepted 28 April 1994

Abstract

A kinetic study of the pyrolysis of polyethylene (HDPE) in a fluidized sand bed reactor
was carried out. The HDPE particles were discharged onto the fluidized bed; in the upper
part of the reactor, the volatiles evolved from primary reactions underwent secondary
cracking reactions. A correlation model was applied to simulate the primary and secondary
reactions, as well as the heat transfer process. The experimental yields of the total gases
obtained in 41 runs performed at 500, 600, 700, 800 and 900°C fitted satisfactorily with the
proposed model. The values of the kinetic parameters of the secondary reactions and the heat
transfer coefficient from the bed to the sample were optimized.

Keywords: Fluidized bed reactor; Kinetic model; Polyethylene; Pyrolysis

1. Iotroduction

The yields of the products obtained from a pyrolysis process are evolved from the
raw material decomposition (primary reactions) and the reactions suffered by the
primary volatiles (secondary reactions). The extension of the secondary reactions
depends on the experimental equipment as well as on the operating conditions. It is
well known that high residence times and high temperatures favor the secondary
reactions.

* Corresponding author. E-mail: gullon@vm.cpd.ua.es.

0165-2370/94/$07.00 0 1994 - Elsevier Science B.V. All rights reserved

SSDZ 0165-2370(94)00806-C
102 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120

The gas yield obtained from the primary reactions only is low, and the following
decomposition of tars and waxes formed in these reactions by means of secondary
reactions leads to the production of a great quantity of gases.
There is not a lot of information in the literature about the kinetics of tar
decomposition from lignocellulosic products. The most representative works on the
thermal cracking of lignocellulosic tars are those presented by Antal [ 11, Diebold
[2], Font et al. [3], Garcia [4], Liden et al. [5] and Boroson et al. [6]. No
information about the cracking of tars and waxes from polyethylene has been
found.
The thermal decomposition of polyethylene is somewhat different from that of
lignocellulosic materials, because the polyethylene melts before its decomposition,
and the reaction can be treated as the decomposition of a liquid.
From the polyethylene pyrolysis, the yields obtained at SOO”C, when the wax
cracking takes place extensively, are the following:

Total gas: 99.72% Methane: 10.04%

Ethane: 3.56% Ethylene: 25.30%
Propane: 0.40% Propylene: 15.61%
Acetylene: 0.07% Butylene: 6.54%
Butane: 0.32% Pentane: 5.05%
Benzene: 5.84% Toluene: 2.19%
Xylenes: 0.04% Styrene: 0.04%

More details of the yields can be found elsewhere [7] and will be published in
another paper.
The thermal decomposition of polyethylene in a thermobalance was analyzed [7].
The heating rates used were 5, 25, 50 and lOO”C/min. The fitting of the experimen-
tal data of the four curves was very good using two different models.
Three reaction scheme:

k, aG1+bA,
IfT P* p a’G, + b’Az

In accordance with experimental results obtained in TG runds, reaction ( 1) and (3)

are considered superficial, whilst reaction (2) is considered to occur in the bulk
mass.
Zero-order kinetic:

PE 5 aGp+bAp

These models are discussed in the following sections.

The aim of this paper is to develop and apply a kinetic model from the HDPE
pyrolysis data obtained in a fluidized sand bed reactor. In the proposed model,
primary and secondary reactions, the surface of the melted particles, and heat
transfer between hot sand bed and sample have been considered.
 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 103

2. Experimental

Pyrolysis was carried out in a cylindrical 18/8 stainless steel reactor. The inert
fluidized bed was sand of 0.105-0.210 mm particle size, calcinated at 900°C and
washed by an acid solution of HCl. The inert gas used was helium at 99.999%
purity.
Heating was achieved by means of a refractory oven. The bed surface tempera-
ture was controlled automatically at five different temperatures: 500, 600, 700, 800
and 900°C. The reactor was not isothermal, showing a temperature gradient from
the sand bed to the top of the reactor. Two chromel-alumel thermocouples were
used to control and measure the temperature profile.

3. Results

Data from 41 experiments of HDPE pyrolysis in a fluidized bed reactor at five

different sand bed temperatures (500, 600, 700, 800 and 900°C) were used to
calculate the kinetic parameters. The mass of sand and the weight of polyethylene
discharged onto the hot bed were modified in each experiment. The mean residence
time depended on the mass of volatiles produced and the volume of the upper part
of the reactor.
Fig. 1 shows the experimental yields of gases obtained vs. the magnitude V/m
(volume of the upper part of the reactor, without sand/mass of the HDPE
discharged onto the bed). When V is constant, the greater the value of m, the
smaller the residence time. When m is constant, the greater the value of V, the
greater the residence time. Note that although V/m is not directly proportional to
the residence time of the volatiles in the non-isothermal upper part of the reactor,
there is some relation between the ratio V/m and the residence time.
In the experiments carried out at 500°C the principal product is a degraded
HDPE, obtained in the solid state. The molecular weight of those HDPE waxes
(analyzed by GPC) is around 300.

4. Kinetic study

In the reactor used in this work two zones can be considered: (a) the fluidized
sand bed where the sample is discharged and at the top of which the primary
reactions take place; (b) a hot zone in the upper part of the reactor where the tars
formed are cracked.
The correlation model used to calculate the secondary kinetic parameters is
similar to that presented by Font et al. [ 31 in their study of the pyrolysis of almond
shells in a fluidized bed reactor. Nevertheless, some modifications in both the data
treatment and the reaction scheme have been carried out on the new material used.
The kinetic model is based on the following assumptions.
104 J.A. Conesa et al. I J. Anal. Appl. Pyrolysis 30 (1994) 101-120

500’1:
%W(pS
100

60 0
___----
0 0

40

20

0 200040006000aOw
v/m Wg)

700%
wO%wp
0
_-+
lA 0
80 . ,,:”
.i

20.

O-
0 20004aOOaooo8000
vhn Wg)

0’
0 2000 4000 MOO 8000 Fig. 1. Variation of yield of total gas vs.
Vh (cc/e) ratio V/m.
 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 105

(1) As a consequence of the primary reaction undergone by the polyethylene

sample discharged onto the bed, a small amount of volatiles (Al’,) is generated in
a small interval (At,). The AV, formed is pushed by the helium flux through the hot
zone above the fluidized bed. In this zone, the volatiles are cracked as a consequence
of the secondary reactions, and the mixture expands. Over the next time interval
(A&), another amount of volatiles (AV,) is generated. This is also pushed by the
helium flux to the top of the reactor. AV, continues rising as its volatiles are pushed
upwards by the helium flux and by the new volatiles increment AL’,. The distance
of any volume element to the top of the sand bed is calculated taking into account
the volume occupied by the elements under it, and this changes with time as a
consequence of helium flow and the expansion of all the volumes due to the
secondary reactions. This process continues until the total sample decomposition and
99.9% of volatiles evolved have left the reactor. Fig. 2 shows the steps considered.
(2) In order to develop the mathematical model, both kinetic and heat transfer
phenomena have been considered. The aspect that have been taken into account, as
well as the basic expressions used in the model, are shown below:

4.2. I. Primary kinetic law

The overall primary decomposition reaction of HDPE can be represented by:
PE+aGp+bAp

-
..
jj::: I’

u
...<.
::
:.+Q
1H* I He I He
t=o t= At t=2 At :t=3 At t=Q At

0, b C d e’
Fig. 2. Steps in the pyrolysis process of HDPE in the fluidiid bed reactor.
106 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) IOI-I.?0

where PE, Gp and Ap refer to the polyethylene, primary gases and primary tars and
waxes respectively. In the mathematical expressions, PE, Gp and A, are the mass
fractions of the corresponding material PE (polyethylene), Gp (primary gas) and
Ap (primary waxes and tars); the values a and b are the yield coefficients, i.e.
product formed (kg) /PE reacted (kg).
Obviously
a+b=l (2)

and

a = G,,, (3)

b = A,,,, (4)
where Gp_ and A,,, are weight fractions that can be formed when all the sample
is decomposed (at time infinity).
It is evident that
a(P& - PE) = G, (5)

b(PE, - PE) = A, (6)

Consequently, at any time

AJG,, = b/a (7)
PE,=l=PE+G,+A, (8)

and

%_ dPE dPE
-GF+ dt (9)
dt --adt=
dA dPE dPE
P=_b
7 = -Awn dt (10)
dt
For the volume of gases formed by the primary reaction (G,), it can be written
that

dVGp
-=- v
dPE
(11)
GP.~ 7
dt
where V, is the volume of gases formed at any moment for a given temperature,
and V~p,m is the maximum value of V, (at time infinity).
For the tars and waxes formed (in the gaseous state at the experimental
conditions, and as liquids .or solids at room temperature), it can be written that

dVA~
-=- v
dPE
(12)
dt AP,~ dt

where VA, is the volume of tars formed and V,,,, is the maximum value of VAp (at
time infinity) at a given temperature.
 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 107

If Vvr is the total volume of volatiles (gases + primary tars and waxes), it can be
written that

v,, = VIZ,+ Y4r (13)

VVP,00 - v,,, + vAp,m (14)
From Eqs. (1 l), (12), (13), and (14), it can be deduced that

-=
dVVP __v .-dPE
dt V&‘,m dt (15)

Eq. (15) is the one considered in the model, and applies to polyethylene decompo-
sition.
For the primary pyrolysis, two different models have been considered [7]:
(a) Three reaction scheme:
aG, + bA,
k,
LP*Ta’Gl+b’A,
kz
No difference in behavior is considered between gases Gi and GZ, and tars A, and
A, as well as in their yields, directly from either P or P*. In this scheme
A, +&=A,
(16)
G, + G2 = G,
and

MdP=-kS1 p
(p + p*> - k2PMo
’ dt
(17)
M dP* P*
0x= +k2J’Mo - k3S cp + p*j

where S is the surface exposed to the surrounding atmosphere, MO is the initial

mass of the sample, and the kinetic constants (k,, k2, k3) vary with the absolute
temperature by the Arrhenius equation:
ki = k, exp( - Ei /RT) i=l, 2, 3 (18)
The overall equation for the polyethylene decomposition can be written as
dPE
-=k,x (1%
dt M,&+k3&&z

where PE is the amount of polyethylene (P + P*) present at any time.

The constants obtained from TG experiments were the following [7]:
ko, = 2.892 x 1019 s-’ me2 kg-’ E, = 171.1 (kJ/mol)

k 02 = 2 . 830 x 1013 s-i E2 = 234.6 (kJ/mol)

ko3 = 2.349 x 16O s-l me2 kg-’ E3 = 195.8 (kJ/mol)

108 J.A. Conesa et al. /J. Anal. Appl. Pyrolysis 30 (1994) 101-120

(b) Zero order kinetic:

kl
PE - aGp+bAp
in which

-d!+,; (20)
0

and
klo = 8.543 x 1018 s-r mm2 kg-’ E, = 164.3 kJ/mol
Note that in a TG apparatus the surface exposed to decomposition is known.
Nevertheless, when the polyethylene sample is discharged onto the hot sand bed,
the polyethylene melts prior to its decomposition and the surface exposed is not
known. To account for this, the parameter exterior surface/initial mass of a particle
(S/M,& is introduced into the model. This parameter has also been optimized.
The TG results indicate that there is no great difference between the two models
at the heating rates mentioned. Nevertheless, in this paper the two models have
been tested, due to the fact that reaction (2) becomes more important at high
heating rates.

4.2.2. Heat transfer between the. sand bed and the sample

Heat transfer processes between the hot sand bed and the sample have been
modeled taking into account the possible differences between bed temperature and
sample temperature. A heat transfer coefficient (U,) has been included in the model
to estimate the actual temperature of the primary decomposition. The expression
used is as follows:
dTp u,S
dt -c, (T,,-T,)=H,!$(T,,-TJ (21)
P

where Tb is the temperature of the fluidized bed, Tp is the actual temperature of the
sample at time t, and S is the external surface of the polyethylene. Owing to
difficulties in modeling (especially for S), HP = U, S/M, C, is considered as a fitting
parameter.
Although the value of 17, can vary as a function of time, it has been considered
constant throughout the process. The parameter HP, therefore, represents a simplifi-
cation to calculate the heat transfer coefficient.

4.2.3. Secondary reaction

G, (secondary gases)
bAp :”
<
” S, (solids, waxes and heavy tars) (22)
According to the suggested model, it is considered that during a small time interval,
a certain amount of primary gases and tars ( Vcr,o and VAp,o, respectively) is
 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 109

generated as a consequence of primary reactions. These compounds are entrained

by the helium flow to the exit of the reactor, undergoing cracking inside the reactor
as a consequence of the secondary reaction.
If the primary tar decomposition is given by Eq. (22), it can be written that
1 dAA, _
--_ (23)
AV, dz
where AV, is the volume reaction element considered, which rises throughout the
reactor, containing: (a) a constant quantity of primary gases AG,,; (b) a quantity
of untracked tars AA,; (c) a quantity of secondary gases AG, generated as a
consequence of tar cracking; (d) a quantity of helium (function of the flux and the
time interval considered). This volume element will vary as a consequence of the
volatile expansion due to secondary reactions. If the evolution of this volume is
known, the situation can be determined and its temperature, therefore, is obtained
from the previously determined temperature profile.
The integration limits of Eq. (23) are
AA,, = AA,,,, when r = 0 (the volume element has been
generated as a consequence of the primary reaction)
and
AA, = AA,,, when z = z, (the volume element leaves the reactor)
Eq. (23) can be written as

dAAP
-
_
- +,I + kz) AA,
dr
The quantity of untracked primary tars can be expressed as a function of the
tenerated tars (AA,,) and of the reaction extension (X,):
AA, = AA& 1 - X,) (25)
From Eqs. (24) and (25):

2 =(k, + kd( 1 - X,)

Eq. (26) defines the kinetics of the secondary reaction as a function of the extent of
reaction of the tars.
If AV,, is the total volume of gases (primary + secondary) that are within a
volume AVR considered, it can be written that
AV,, = AVGp,o + AV,, + AV,, (27)
and also

AV~,_~_AA&l--s)
(28)
PAP PAP

where pAp is the density of the primary tars.

110 J.A. Conesa et al. / J. Anal. Appl. Pyrolysis 30 (1994) 101-120

For each interval considered, at any temperature, it can be written that

A&2% (29)
PGs PGs

where pGs is the density of the secondary gases, and the ratio ksl /(k,, + ks2)
represents secondary gases formed (kg)/primary tar formed (kg).
Combining Eqs. (27) -( 29) :

AV,,,==AVG,,o+hAp30(1 -‘I+
PAP PGs

AAp3o
= AvGp.0 +
(30)

Bearing in mind that

AA,,
A VA,, = d (31)
PAP

and

AGpo
AL,‘,,0 =A (32)
PGP

Eq. (31) can be written as

-A+AA, o AAp,o ( )-
PGs
k,
k,, + ks2

AVW = (AVGP,O + AVA,o) 1 + -& PAp (33)

AG,o AA,,
d+d

PGp PAp

Since

AV,,, = AV,,,o+ AV,,,o (34)

and defining

AA,
------+ o

PAP PGs
cI= (35)
AGP,O ( AAP.0

PGp PAp
 J.A. Conesa et al. /J. Anal. Appl. Pyrolysis 30 (1994) 101-120 111

Eq. (33) can be transformed to

AVv, = AJ&,(l+ mx,) (36)

Eq. (36) defines the expansion of total volatiles (primary plus secondary) as a
consequence of the cracking of tars in the secondary reaction.
Bearing in mind that by the primary reaction

AG,,,o= (0) A-%,, (37)

and taking into account the molecular weights of the tars, primary gases and
secondary-gases (MAP, MGp , Mos respectively), Eq. (35) can be rewritten as:

(38)

4.2.4. Heat transfer between the volatiles and the reactor wall

The volatiles flow through the reactor from the bed to the top of the reactor. The
temperature profile along the reactor was measured when only the inert gas flowed
through it. This profile is a consequence of the heat transfer between the walls of
the reactor and the gas which is flowing. The profile can be modified in the presence
of volatiles. Bearing these aspects in mind a correction factor has been introduced
for any volume:

where Tj is the real temperature of the volume considered, and TR is the reactor
temperature according to the temperature profile measured at the position of the
volume of volatiles.

5. Correlation of experimental data

The experimental data of the total gas yield for 41 runs [7] were correlated by the
suggested models.
The objective function considered was

0.F. = i (Yexpj- L&2

j=l

where the experimental yield was calculated as

gas analyzed (g)
yexpj
= polyethylene sample (g)
(41)
112 J.A. Conesa et al. / J. Anal. Appl. Pyrolysis 30 (1994) 101-120

The gases analyzed were methane, ethane, ethylene, propane, propylene, acetylene,
butane, butylene, pentane, benzene, toluene, xylenes and styrene.
The calculated yields according to the simulation program were obtained by the
following equation:

Yca,cj
= : A%, +
i=l
I?A~p,cpsi
i=l
(42)

where the sum comprises all the intervals considered (i), and where AG,,,i and AY&~
are the quantities (g) of gases and primary tars generated in the “i” interval per gram
of polyethylene discharged, respectively. The sum considers 150 intervals (it has been
proved that the same result is obtained with a number of intervals greater than 150).
The second part of the sum in Eq. (42) represents the quantity of gases generated
from the primary tars:

and consequently

However, the mean volatile residence time can be defined as

where Vvp,i is the volume of total primary volatiles in the i interval, and

I’,, = 5 Avv,i (46)

i=l

In Eq. (25), ri is the time required by the element i to flow through the empty part
of the reactor from its generation. Note that Z refers to the mean residence time of
volatiles in the upper part of the reactor, where cracking takes place. This mean
residence time of volatiles is different from the total mean residence time, which also
includes the period of time from the discharge of the material to the generation of
the different elements by the primary reactions.
Eqs. (41) and (42) have been used to calculate the value of the objective function.
The optimized variables were the following:
- modulus HP, referring to the heat transfer sample-sand bed;
- correction fractor H, of the temperature in the upper part of the reactor;
- activation energy of the two secondary reactions (E,,IR and Es2/R);
- secondary kinetic constants at 1000 K (k,,,,,, and ks2,iW0& (since inter-
relation between activation energy and kinetic constant at 1000 K is lower than
inter-relation between the activation energy and the pre-exponential factor);
- ratio between the surface and the initial mass of a particle (S/M,,,).
The optimization method was the Flexible Simplex [8].
 J.A. Conesa et al. / J. Anal. Appl. Pyrolysis 30 (1994) 101-120 113

In order to carry out the calculations, the following data were considered in each
experiment.
(1) Volume of primary gases and tars generated at the temperature of the
sand bed. These values were estimated from the data obtained in the Pyroprobe
1000. The quantity of heavy tars was calculated by difference, because the TG
data provide values of the primary kinetic constants but not information about
the amounts of tars and gases. An average molecular weight of tars of 320 kg
kmol-’ was considered from an analysis of waxes obtained in the 500°C experi-
ments.
(2) Experimental total yield of gases.
(3) Temperature of the fluidized sand bed.
(4) Temperature profile in the upper part of the reactor.
(5) Flux of helium and section of the reactor.
(6) Weight of polyethylene discharged.
(7) Average molecular weight of the gases analyzed.
(8) Average molecular weight of the secondary gases, obtained from total gases
analyzed in the fluidized bed reactor and the primary gases in the Pyroprobe 1000.
(9) Value of the coefficients a and b of the primary reaction (Eq. l), calculated
as G,,, and A,,,.
The mean value of the coefficient a (where b = 1 - a), the average molecular
weight of the gases analyzed, and the average molecular weight of the primary
gases, were correlated with temperature. Figs. 3-5 show these variations. The
correlations obtained were used in the simulation program.

a coefficient
0.4

0.3 -

0.2 -

0.1 -

0
400 500 600 700 800 900 11
Temperature CC)

Fig. 3. Variation of coefficient a with temperature.

114 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120

Mean molecular weight of analyzed gases

60

50- .

401 \ . .

30
.

20 -

10 -

0’
400 500 600 700 800 900 Ii00
Temperature CC)

Fig. 4. Variation of average molecular weight with temperature of analyzed gases in the fluidized bed
reactor.

lean molecular weigM of primary gases

50

40

30

20

10

OL
400 500 600 700 800 900 1000
Temperature (%)

Fig. 5. Variation of average molecular weight with temperature of primary gases in the Pyroprobe
1000.
 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 115

6. Analysis of the calculated parameters

Table 1 shows the results of the correlations for the two models used. Table 1
also shows the objective function (OX) and the variation coefficient (V.C.), defined
as

J
O.F.
IZ experimenr-n parameters x 1OO
V.C. (%) = (47)
=P

where FeXpis the mean value of the experimental yields of total gases that were
considered in the fitting (n experiments = 41).
For the spherical particle used of 5 mm diameter with a density of 940 kg/m3, the
value of the ratio S/A+ is 1.27 m*/kg. In the model, the parameter obtained varied
between 6.01 and 6.32 m*/kg (depending on the model). It is observed that the
value S/M,, obtained in the correlation is greater than the value S/MpO for the solid
particle. This difference could be due to the fact that the polyethylene particles melt
prior to their decomposition, and the ratio SM,,,, is therefore greater than in the
solid state.
The value of the modulus HP is, 5.2 x IO-* SK’ or 8.3 x lo-* s-i, depending on
the model used. Considering a 5 mm average diameter particle (that has not
melted), a density of 940 kg rne3, a value of C, of 3762 J/kg “C, values of U, = 153
and 244 J/s m* K can be obtained from models 1 and 2 respectively.
The value of H, is 2.8 or 3.1 SK’ depending on the model. This value is high
enough to rule out any significant differences between the temperature prior to and
after the discharge of the sample.
Fig. 6 shows the kinetic constants for some materials at different temperatures.
The values represented correspond to those obtained by Antal [l] for tar cracking
from cellulose, Diebold [2] for wood pyrolysis, Liden et al. [5] for biomass, Font et
al. [3] for almond shells, and the present work. As can be seen in Fig. 6, the
activation energies are similar to those obtained by Antal for the cracking of
cellulose tars, assuming also two parallel reactions for the cracking of tars.

Table 1
Values of optimum parameters and objective function

Case 1 (three reactions) 2 (zero order)

S/M,, (m2/k) 6.32 6.01

HP (s-l) 5.29 x 10-Z 8.28 x lo-*
Hs (s-l) 3.01 2.79
k s*.1mK1 ‘s-:’ 9.93 11.17
k;S.;m$g- 1 3.09 2.85
23745 23616
-J&/R (K) 28397 27935
O.F. 0.141 0.094
V.C. (%) 10.67 8.72
116 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120

,ooo KS(l/S)
100 SXX
fy&Qfp
1

IO1 l ~ ~ ~ ~
0.
0.1 . 0. oooxxx -di&
l 0 X
.
0.01
0.001
l *.
.
0 0
0
X
0
X

. 0
.
0.0001 .
.
.
O.OOOQ1~” ” ” ” ” ” I ” ” ” 1””
0.8 0.9 1 1.1 1.2 1.3 1.4
1000/T (1000/K)
l Antal + Diebold * Liden
n Font X Present work reaction 1 0 Present work reaction 2

Fig. 6. Kinetic constants for tar decomposition.

Nevertheless, the ranges of the kinetic constant ksl and k,, are close to those
proposed by Diebold [2], Liden et al. [ 51 and Font et al. [3], in the decomposition
temperature range.
Fig. 7 shows very good agreement between the yields calculated by model 2 vs.
the experimental ones. Fig. 8 represents the calculated and experimental yields,
together with the Pyroprobe results, vs. the calculated residence time. If this Figure
is compared with Fig. 1, it can be seen that the V/m value is not totally
proportional to the residence time. Fig. 7 shows less dispersion than that in Fig. 1.
Nevertheless, this residence time is not representative of the tar cracking because
the reactor is not isothermal. Similar results are obtained for model 1.
In accordance with the proposed model and taking into account the optimized
parameters, the variation of temperature and the extent of the primary reaction vs.
time were simulated. Fig. 9 and 10 show the ratio total gas flow/helium flow, and

0 20 40 80 80 loo
Experimental yield

Fig. 7. Calculated vs. experimental yields of total gases.

 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 117

T profile: 300-500 =‘C T profile: 300-600 “c

%Wgrrs
100

0 2 4 8 8 10 12 14 16
Residence time (s)

T profile: 300-700 “c T profile: 30O-K10 “c

loo%lotal@= 100%totalP
lo

60
0 0

111
80. i”,
0
60

40

20 20

0 OL ’ . ’
0 2 4 6 8 10 12 14 16 0 2 4 6 0 IO 12 14 16
Resiince time (a) Flesidence time (s)

‘11 , , 1 Fig. 8. Calculated and experimental

0 2 4 6 8 10 12 14 16 yields, together with the Pyroprobe
Residence time (s) I results, vs. calculated residence time.
118 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120

x (%)
T(K)
800
100
800
80 -
- 700
80 -

40 -

20 -

0 /
15 20 25 30 35 40
time (s)

Fig. 9. Temperature and extent of primary reaction vs. time of reaction.

251
20 .-

IO -

5-

0 /
15 20 25 30 35 40
time (s)

Fig. 10. Total gas flow/helium flow ratio vs. time of reaction.

the temperature evolution of a particle and extension of primary reaction, for

run no. 26 (T = 7OO”C, 300 g sand and 1.487 g PE) with model 2. As can be seen
from Fig. 10, the production of gases increases as the temperature increases, until
all the PE is decomposed. This is due to the primary reaction, in which the gas
production increases continuously with temperature, independent of the mass of the
sample.

7. Conclusions

On considering the kinetic law corresponding to the primary decomposition,

obtained in TG runs, the experimental results obtained in the fluidized bed reactor
with cracking in the upper part of the reactor fit satisfactorily to a model with two
 J.A. Conesa et al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120 119

parallel reactions:
Secondary gases
Primary tars and waxes :”
<
” Solids, waxes and heavy tars
The activation energies are around 196.3 and 232.2 kJ/mol for reactions 1 and 2
respectively. The values of the kinetic constant at 1000 K are around
k sl,lmK = 9.93-11.17 s-l
k s2,1mK = 3.09-2.85 s-r

depending on the kinetic model used.

Acknowledgments

Support for this work was provided by CYCIT-Spain, Research project AMB93-
1209.

List of symbols

primary gases (kg)/HDPE decomposed (kg)

mass fraction of primary tars and waxes formed
mass fraction of tars and waxes that can be formed at time
infinity
primary tars and waxes (kg) /HDPE decomposed (kg)
calorific capacity of polyethylene (J/kg “C)
activation energy of the primary reaction i (kJ/mol)
activation energy for the secondary reactions 1 and 2, respec-
tively (kJ/mol)
GP mass fraction of primary gases formed
G mass fraction of gases that can be formed at time infinity
AX volume element of secondary gases formed in the reaction
volume AVR(m3)
optimized parameter related to the heat transfer to the particle
(s-l)
optimized parameter related to the heat transfer to the volatiles
(s-l)
4 kinetic constant of the primary reaction i (s-l)
k, pre-exponential factor of the kinetic constant of the reaction i
(s-9
k,, 9 ks, kinetic constant for the secondary reactions 1 and 2, respec-
tively (s-r)
k sl,lOOOK~ k s2,lOOO K kinetic constant at 1000 K for the secondary reactions 1 and 2,
respectively (s - ‘)
molecular weight of primary tars (kg/kmol)
120 J.A. Conesa ef al. 1 J. Anal. Appl. Pyrolysis 30 (1994) 101-120

MGP molecular weight of primary gases (kg/kmol)

MGS molecular weight of secondary gases (kg/kmol)
MPO
initial mass of a particle (kg)
O.F. objective function
PE mass fraction of polyethylene not decomposed by primary
reaction
s surface of PE exposed to the surrounding atmosphere (m’)
Ati time interval (s)
u, heat transfer coefficient for the primary reaction (J/s m2 K)
V.C. variation coefficient
Vim volume of the upper part of the reactor/mass of polyethylene
discharged onto the bed (cm’/g)
VAP volume of tars and waxes formed at a given temperature (m’)
VAp,m volume of tars and waxes formed at a given temperature and at
time infinity (m3)
VGP volume of gases formed at a given temperature (m3)
VGPm
volume of gases formed at a given temperature and at time
infinity ( m3)
AVi volatiles generated by the primary in the time interval Ati (m’)
AV, volume of reaction element considered (m3)
A VW total volume of gases (primary + secondary) in a volume AVR
Cm’)
VVP volume of volatiles (gases + tars + waxes) (m3)
VVP,rn volume of volatiles (gases + tars + waxes) at time infinity (m3)
x, extent of secondary reaction
YCdC
j calculated yield in experiment j
yexpj experimental yield in experiment j

Greek letters

PAP
density of primary tars and waxes (kg/m3)
PGS density of secondary gases (kg/m3)
z residence time (s)

References

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