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J. Anal. Appl. Pyrolysis 81 (2008) 127–132

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Kinetic modelling of tyre pyrolysis in a conical spouted bed reactor

Martin Olazar, Gartzen Lopez *, Miriam Arabiourrutia, Gorka Elordi,
Roberto Aguado, Javier Bilbao
University of the Basque Country, Faculty of Science and Technology, Department of Chemical Engineering, P.O. Box 644, E48080 Bilbao, Spain
Received 27 June 2006; accepted 25 September 2007
Available online 29 September 2007

Abstract
A novel kinetic model has been proposed for the thermal pyrolysis of tyres. The model is based on a reaction scheme that considers an
intermediate lump and parallel reactions for the formation of the different product lumps. Seven lumps have been taken, which are gas (C4), non-
aromatic liquid (C5C), aromatics (C), tar (C11+), char (low grade carbon black), intermediate and the original tyre. The kinetic data have been
obtained in a pilot plant provided with a conical spouted bed reactor. The inert gas used is nitrogen and the temperature has been varied from 425 to
610 8C. Discontinuous runs have been carried out for obtaining the kinetic data, and the product stream has been analysed on-line at different
reaction times, thereby monitoring the evolution with time of mass fraction of the different components. The kinetic model gives reasonable
predictions for lump yields.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Pyrolysis in spouted bed; Kinetic study; Scrap tyre

1. Introduction
Waste tyres are a serious environmental problem due to the
potential risk involved in their deposition in a dumping site.
Thus, their deposition is not a suitable solution mainly due to
the volume of residues, which according to estimations will
continue increasing even at a higher rate for next decades. At
present, 2.5 million tonnes per year of waste tyres are generated
in Europe, a similar amount in USA and approximately 1
million tonnes in Japan [1]. Consequently, urgent solutions are
required for their valorization.
There are several routes for upgrading waste tyres, which are
mainly based on two strategies: energy production by
incineration or combustion [2] or recovery of their components
by hydrogenation [3], liquefaction [4] or pyrolysis.
Pyrolysis is considered as one of the more feasible solutions
that may be economically profitable at large scale. The interest
is centred on the fact that the products obtained by this process
may be easily handled, stored and transported and they may be
transformed in other units that are not near the recycling one
* Corresponding author.
E-mail address: gartzen555@yahoo.es (G. Lopez).
0165-2370/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2007.09.011
[5]. The pyrolysis liquid product may be used directly as fuel or
may be added to a refinery feed. Furthermore, interesting
chemical products, such as benzene, toluene and xylenes and
limonene [6–9] are obtained. The gases obtained may be used
as fuel for making the process autothermal. The carbonaceous
material may be used as a quality fuel, or it is a suitable raw
material for carbon black or active carbon [10].
Several authors have studied the kinetics of tyre pyrolysis by
means of techniques based on TG/DTG [11–14]. These studies
allow for identifying the different types of rubber in the tyre,
based on the results of its thermal decomposition. Nevertheless,
most of these studies have approached solely the kinetics of
rubber decomposition (devolatilization), without establishing
the kinetic schemes for the formation of secondary products.
Furthermore, the equipment used operates under conditions
that are different to those of an industrial oven, where particle
heating is almost instantaneous and gas-particle contact is
much more turbulent. Conesa et al. [15] show the importance of
pyrolysis severity on product distribution, which explains the
difference between the results in a microreactor, fluidized bed
and horizontal oven. In view of this, progress in the kinetic
modelling of tyre pyrolysis is essential in order to obtain kinetic
equations that are useful for the design and simulation of
commercial reactors. In fact, virtually no kinetic studies have
128 M. Olazar et al. / J. Anal. Appl. Pyrolysis 81 (2008) 127–132
Nomenclature
Dc, Di, Do diameter of the cylindrical section, the con-
tactor base and the gas inlet, respectively (L)
EOF error objective function defined in Eq. (9)
Hc, Ho, HT height of the conical section, stagnant bed
height and total reactor height, respectively (L)
ka, kg, ki, kia, kic, kit, kl reaction constants of the steps of
the kinetic scheme Fig. 3 (T1)
nexp, nl number of experimental points and of lumps used
for the fitting
Xa, Xc, Xg, Xi, Xl, Xt yields of aromatics (C10), carbon
black, gas (C4), intermediate, non-aromatic
liquid (C5–C10) and tar (C10+), respectively
Xi,j, Xi(cal),j experimental and calculated values for i lump
conversion at j reaction time
Xn tyre conversion
Wo W initial tyre mass and tyre mass at a given time.
Greek letter
g angle of the conical section (u)
been carried out in a gram scale or bigger plant. The studies
carried out at pilot or industrial scale in fixed bed reactors [16],
fluidized bed reactors [17–21], moving bed reactors under
vacuum [22,23] and rotary ovens [24,25] focus on the
determination of the effect of reaction conditions on the yield
of the different fractions.
In this paper, a pilot plant provided with conical spouted bed
reactor has been used for the kinetic study. This reactor has
been designed from hydrodynamic studies carried out with
different solids and reactor configurations [26,27]. Previous
studies have proven that this reactor is especially suitable for
the treatment of materials that are irregular or of sticky nature.
Thus, benzyl alcohol polymerisation [28], pyrolysis of biomass
[29,30] and pyrolysis of waste plastics [31] have carried out
successfully. Versatility in the gas residence time (from 20 ms
to a few seconds) and turbulent gas–solid contact are the main
features of this reactor.
2. Experimental
Based on hydrodynamic studies in a cold unit and on the
experience acquired in prior pyrolysis of other type of agroforest
residues and plastics [29–31] a pilot plant for pyrolysis and
gasification of scrap tyre has been designed, built and fine tuned.
Fig. 1 shows a diagram of the unit, which consists of the
following components: (1) solid feeder; (2) a system for feeding
the inert gas; (3) the pyrolysis reactor; (4) a system for fine
separation from the gaseous stream; (5) condensers and filters
for liquid product collection; (5) a system for the analysis by
gas chromatography of the gases produced; (6) a control unit
(Labtech under Windows). The char (carbon black) outlet pipe
has been designed for continuous operation and has been closed
for carrying out the discontinuous operation required for the
kinetic study.
Fig. 1. Diagrammatic representation of the pyrolysis unit.
The reactor is the main component of the unit and is of
conical geometry provided with an upper cylindrical section.
The total height of the reactor, HT, is 34 cm, the height of the
conical section, Hc, 20.5 cm, and the angle of the conical
section, g, 288. The diameter of the cylindrical section, Dc, is
12.3 cm, the diameter of the base, Di, 2 cm and the gas inlet
diameter, Do, 1 cm. These dimensions guarantee bed stability in
a wide range of process conditions, particularly regarding gas
velocity, and they have been established in previous hydro-
dynamic studies [26,27]. The hydrodynamic regime may be
changed from that corresponding to the minimum spouted bed
to a vigorous jet spouted bed (or dilute spouted bed), with a
wide transition regime between both [26,32]. This implies great
versatility in the gas–solid contact conditions, especially in the
gas residence time. Consequently, starting with a given stagnant
bed height, Ho, and increasing the gas flowrate, the residence
time may be decreased from a few seconds to values near
20 ms. This fact, together with an excellent heat transfer
capacity, makes this reactor especially suitable for flash
pyrolysis processes.
Below the reactor there is a cartridge containing a ceramic
resistance, which is inside a metallic casing and thermally
insulated. This resistance heats the nitrogen stream up to the
reaction temperature, which is measured with a thermocouple
placed at the upper part of the resistance (below the inlet of
the reactor). In the conical section of the reactor there is another
resistance surrounding the wall of this section, which is
controlled by measuring the temperature at a point near the wall
by means of another fixed thermocouple. Furthermore, the
reactor is insulated in order to minimise energy loss.
The main components of the tyre material studied are (in
wt.%): natural rubber (SMR 5CV), 29.59; styrene–butadiene
rubber (SBR 1507), 29.59; carbon black (ISAF N220), 29.59.
Other components are (in wt.%): stearic acid, 0.59; IPPD (n-
isopropyl-n0 -phenyl-p-phenylenediamine), 0.89; zinc oxide,
2.96; phenolic resin, 2.37; sulphur, 0.89; CBS (n-cyclohexyl-2-
benzothiazol-sulfenamide), 0.89; H-7 (hexamethylentetra-
 M. Olazar et al. / J. Anal. Appl. Pyrolysis 81 (2008) 127–132
mine), 0.18; PVI (n-cyclohexylthio)-phthalimide), 0.12; aro-
matic oil, 2.37. The density is 1140 kg m3 and the high
calorific value (determined in a Parr 1356 isoperibolic bomb
calorimeter) is 38,847 kJ kg1. This material has been ground
to a particle size below 1 mm.
The nitrogen flowrate entering the reactor was 1.2 times that
corresponding to the minimum spouting velocity, which
corresponds to 6.5 l/min at 500 8C and varies within a range
depending on temperature.
The bed was initially made up of 15 g of 1 mm sand and 2 g
of tyre material. The tyre amount used allows for obtaining a
homogeneous mixture in the bed and minimizing the time
required for stabilising temperature. The tyre material was fed
as a pulse once the temperature of the sand bed was
homogeneous. Runs have been carried out at the temperatures
of 425, 500, 550 and 610 8C. Small samples of volatile reaction
products (condensable + non-condensable) are taken from the
stream at the reactor outlet and are monitored by means of a gas
chromatograph (Agilent, GC 6890) provided with flame
ionization detector (FID) and thermal conductivity detector
(TCD). More than 150 compounds have been identified at the
outlet stream by a mass spectrometer (Shimadzu UP-2010S).
The calculation of the amount of each individual compound
produced at a given time has been based on the ratio between
the chromatographic area of this product at this time and the
total chromatographic area of the product for the whole reaction
time. The weight loss up to a given time has been calculated
from the ratio between the cumulative chromatographic area of
all the products up to this time and the total chromatographic
area of all the products. Calibration standards have been used in
this calculation procedure.
3. Results and discussion
3.1. Experimental results
The evolution of the mass fraction of the different lumps
with time has been obtained carrying out batch runs at 425, 500,
550 and 610 8C. Five lumps have been monitored, which are
non-degraded tyre, non-condensable gases (containing hydro-
carbons in the C1–C4 range), liquid (containing C5–C10 non-
aromatics), aromatics (containing C5–C10 single-ring aromatic
hydrocarbons) and, finally, tar (containing C11+ hydrocarbons
both aromatic and non-aromatic).
Fig. 2 shows the evolution of the yield of the different lumps
with temperature in the range studied. It also shows the
evolution of the char fraction, which is the non-pyrolysable
fraction at each temperature. As it is observed, there is a clear
trend for the liquid and tar fractions, which decrease with
temperature, whereas the reverse is true with the aromatic and
gas fractions.
3.2. Kinetic modelling
The reaction scheme proposed for the thermal pyrolysis of
tyres consists of seven lumps, namely, tyre, gas (C4), non-
aromatic liquid (C5–C10), aromatics (C10), tar (C11+),
129
Fig. 2. Evolution of the mass fraction of the different lumps with temperature.
intermediate and char (low grade carbon black). This grouping
into lumps is interesting in order to contemplate a future
valorization of volatile products, which are classified as
aromatic and non-aromatic within the gasoline fraction
(C5–C10) and heavier hydrocarbons (tar, C11+) that are of
lower interest as fuel. The intermediate lump has been
considered in order to explain the evolution of the lumps of
tar and aromatics, given that the formation of these lumps takes
place subsequent to that of gases and liquid. The proposal of an
intermediate in the pyrolysis scheme has already been carried
out by Leung and Wang [13] in order to fit the devolatilization
data obtained in a thermogravimetric device.
This kinetic scheme considers carbon black as another lump,
which is a function of temperature. In fact, carbon black is not a
compound forming throughout time, but rather is the fraction of
the original tyre that does indeed undergo degradation.
Specifically, this situation only takes place at low temperatures
(below 400 8C) and, at high temperatures, condensation of
heavy aromatic hydrocarbons on the carbon black may also
occur. Nevertheless, in the conical spouted bed reactor, the
residence time is very short (around 50 ms) and the char
fraction has a limited dependence on temperature, because
condensation reactions are insignificant.
In this kinetic scheme made up of parallel reactions, the
reaction constants kg, kl, ka and ki are those corresponding to the
primary reaction steps to give gas, liquid, aromatics and
intermediate; the reaction constants kit, kia and kic are the
constants of the reactions yielding aromatics, tar and carbon
black from the intermediate lump. A consideration to be taken
into account for the kinetic modelling of pyrolysis in a conical
spouted bed reactor is the fact that the volatiles (condensable
and non-condensable) formed at each position of the reactor are
continuously carried by the inert gas stream fed into the reactor.
Tyre conversion, Xn, has been defined as the weight loss by
mass unit of the initial amount of tyre:
Wo  W
Xn ¼ (1)
Wo
130 M. Olazar et al. / J. Anal. Appl. Pyrolysis 81 (2008) 127–132

where W0 is the initial mass of tyre and W is the mass at a given Table 1
Values of frequency factor and apparent activation energy obtained for the
time. Mass balances for each one of the seven lumps in
constants of the model
unsteady state give the following expressions:
Reaction Frequency Activation
dX n factor (s1) energy (kJ/mol)
¼ ðkg þ kl þ ka þ ki Þ ð1  X n Þ (2)
dt Tyre to intermediate 6.82  101 46.09
dX g Tyre to gas 3.52  107 63.08
¼ kg ð1  X n Þ (3) Tyre to liquid 1.30  101 40.06
dt Tyre to aromatics 5.35  103 89.26
Intermediate to aromatics 5.00  101 36.33
dX l
¼ kl ð1  X n Þ (4) Intermediate to tar 2.36  103 14.12
dt Intermediate to char 4.79  101 20.50

dX a
¼ ka ð1  X n Þ þ kia X i (5)
dt
subroutine ode45 and optimisation has been carried out by the
dX t subroutine fminsearch.
¼ kit X i (6)
dt
3.3. Results of the model
dX c
¼ kic X i (7)
dt
Table 1 shows the values obtained for the kinetic parameters
dX i for the formation of intermediate, gas, liquid, aromatics from
¼ ki ð1  X n Þ  kia X i  kit X i  kic X i (8) tyre and aromatics, tar and carbon black from the intermediate.
dt
As it is observed, the reactions of formation of aromatics and
where Xg, Xl, Xa, Xt, Xc and Xi are the yields of each one of the
gas have higher apparent activation energies than those of
lumps included in the kinetic scheme shown in Fig. 3.
formation of liquid and tar, as their formation is favoured at
By simultaneously solving Eqs. (2)–(8), the theoretical
high temperatures, Fig. 2.
values for the evolution of the mass fraction with time for the
The adequacy of the model proposed is shown in Fig. 4, in
seven lumps are obtained. The kinetic parameters of best fit to
which the calculated and experimental values of yields are
this model have been determined by fitting the calculated values
shown. As it is observed, the fitting is excellent, which is also
to the experimental ones. For that purpose, an error objective
evidenced by the low value obtained for the objective function
function has been minimised. This has been defined as the ratio
(2.1  104).
between the sum of squares of the differences between
The validity of the model for predicting the evolution of the
experimental and calculated values and the number of degrees
mass fraction of the different lumps with time is shown in
of freedom:
Figs. 5–8, corresponding to the four temperatures studied.
Pnl Pnexp 2
i¼1 j¼1 ðX i; j  X iðcalÞ; j Þ
As it is observed, the model is able to predict the evolution of
EOF ¼ (9) all the lumps, including aromatics and tar. In fact, a model
nl nexp
based on a kinetic scheme made up of only primary reactions
where Xi(cal),j are the values calculated for the conversions and [33] is able to predict the yields of all the lumps, but cannot
Xi,j are the experimental values, nl is the number of lumps used predict the evolution of aromatics and tar, as the lumps of
for the fitting, and nexp is the number of experimental points
(reaction times for which mass fractions have been deter-
mined).
Experimental results obtained in all the runs carried out for
different reaction times and different temperatures have been
considered in the determination of the EOF defined by Eq. (9).
Accordingly, a programme has been written in Matlab, the
set of differential equations have been solved by means of the

Fig. 4. Adequacy of the fitting between the experimental and calculated values
Fig. 3. Diagram of the kinetic model for the pyrolysis of scrap tyre. of the yields corresponding to five lumps (gas, liquid, aromatics, tar and char).
 M. Olazar et al. / J. Anal. Appl. Pyrolysis 81 (2008) 127–132
Fig. 5. Comparison of experimental and calculated evolutions of the mass
fractions of the different lumps with time at 425 8C. Lines: calculated; points:
experimental.
Fig. 6. Comparison of experimental and calculated evolutions of the mass
fractions of the different lumps with time at 500 8C.
Fig. 7. Comparison of experimental and calculated evolutions of the mass
fractions of the different lumps with time at 550 8C.
131
Fig. 8. Comparison of experimental and calculated evolutions of the mass
fractions of the different lumps with time at 610 8C.
aromatics and tar begin to form when the tyre is partially
degraded, and not from the initiation of degradation. The
inclusion of an intermediated lump in the reaction scheme,
Fig. 3, is the key for a suitable prediction of the evolution of
these lumps and explains the delay in their formation.
The results obtained at the lower temperature studied,
425 8C, are those of poorer fitting (Fig. 5). This temperature is
slightly lower than the minimum commonly established for the
valorization of polymeric wastes by pyrolysis at industrial scale
(450 8C) and is close to the value theoretically deduced by Di
Blasi [34], 407 8C, for the fast pyrolysis of natural polymers,
such as cellulose, under conditions in which there are no heat or
mass transfer limitations.
Due to this thermal limitation in pyrolysis processes, and
particularly in tyre pyrolysis, numerous studies in the literature
[35–38] have shown that the frequency factor and apparent
activation energy change when a given thermal level is
exceeded; that is, above a given decomposition degree when
dynamic experimentation is carried out in thermobalance.
Accordingly, the values of the kinetic constants obtained at the
lowest temperature used in this study (425 8C) should be treated
independently, together with values corresponding to similar
temperatures, in order to obtain the frequency factor and
apparent activation energy of this first step and even the
transition temperature between the first and second steps.
Nevertheless, in order to have a simple tool for the industrial
design of this pyrolysis technology, the same treatment has
been given to all available data, accepting that this decision
involves a degree of error in the kinetic parameters determined
in this way.
4. Conclusions
A kinetic scheme of seven lumps has been proposed, and it
satisfactorily predicts the evolution of product distribution in
tyre pyrolysis in a conical spouted bed reactor. Reaction
products have been grouped into lumps that allow for assessing
their interest depending on process conditions. The kinetic
132 M. Olazar et al. / J. Anal. Appl. Pyrolysis 81 (2008) 127–132

scheme contemplates an intermediate to explain the delay [12] O. Senneca, P. Salatino, R. Chirone, Fuel 78 (1999) 1575.
[13] D.Y.C. Leung, C.L. Wang, J. Anal. Appl. Pyrol. 45 (1998) 153.
observed in the formation of aromatics and tar. The kinetic
[14] J.H. Chena, K.S. Chenb, L.Y. Tong, J. Hazard. Mater. B84 (2001) 43.
scheme proposed consists of four primary reactions in parallel, [15] J.A. Conesa, A. Fullana, R. Font, Energy Fuels 14 (2000) 409.
whose reactant is the original tyre, and another three secondary [16] S. Ucar, S. Karagoz, A.R. Ozkan, J. Yanik, Fuel 84 (2005) 1884.
reactions (also in parallel) whose reactant is the intermediate. [17] W. Kaminsky, Resour. Recov. Conserv. 5 (1980) 205.
The interest of the kinetic scheme and the corresponding [18] J.A. Conesa, A. Marcilla, R. Font, J.A. Caballero, J. Anal. Appl. Pyrol. 36
parameters lies in the consideration of product lump yield (1996) 1.
[19] W. Kaminsky, C. Mennerich, J. Anal. Appl. Pyrol. 58–59 (2001) 803.
evolution with time. The conditions of bed isothermicity and [20] A. Ono, M. Kurita, T. Nagashima, M. Horio, Waste Manage. 21 (2001)
excellent heat transfer between the phases in the spouted bed 451.
reactor ensure the interest of the kinetic result for its use at [21] X. Dai, X. Yin, C. Wu, W. Zhang, Y. Chen, Energy 26 (2001) 385.
larger scale. The values of the apparent activation energy for the [22] C. Roy, H. Darmstadt, B. Bellanal, C. Amen-Chen, Fuel Process. Technol.
50 (1997) 87.
different steps in the kinetic scheme range from 15 to 90 kJ/
[23] C. Roy, A. Chaala, H. Darmstadt, J. Anal. Appl. Pyrol. 51 (1999) 201.
mol, being higher for the formation of gas and C10 aromatics. [24] S.Q. Li, Q. Yao, Y. Chi, J.H. Yan, K.F. Cen, Ind. Eng. Chem. Res. 43
(2004) 5133.
Acknowledgements [25] C. Dı́ez, M.E. Sánchez, P. Haxaire, O. Martinez, A. Morán, J. Anal. Appl.
Pyrol. 74 (2005) 254.
This work was carried out with the financial support of the [26] M. Olazar, M.J. San Jose, A.T. Aguayo, J.M. Arandes, J. Bilbao, Ind. Eng.
Chem. Res. 31 (1992) 1784.
Ministry of Environment of the Spanish Government (Project [27] M. Olazar, M.J. San Jose, A.T. Aguayo, J.M. Arandes, J. Bilbao, Ind. Eng.
5.3-085/2005/3-B) and of the Ministry of Industry of the Chem. Res. 32 (1993) 1245.
Basque Government (Project IE05-149). [28] M. Olazar, M.J. San Jose, G. Zabala, J. Bilbao, Chem. Eng. Sci. 49 (1994)
4579.
References [29] R. Aguado, M. Olazar, M.J. San José, G. Aguirre, J. Bilbao, Ind. Eng.
Chem. Res. 39 (2000) 1925.
[30] M. Olazar, R. Aguado, A. Barona, J. Bilbao, AIChE J. 46 (2000)
[1] A. Aranda, R. Murillo, T. Garcı́a, M.S. Callén, A.M. Mastral, Chem. Eng. 1025.
J. 126 (2007) 79. [31] R. Aguado, M. Olazar, M.J. San José, B. Gaisán, J. Bilbao, Energy Fuels
[2] V.K. Sharma, F. Fortuna, M. Mincarini, M. Berillo, G. Cornacchia, Appl.
16 (2002) 1429.
Energy 65 (2000) 381. [32] M. Olazar, M.J. San José, R. Aguado, B. Gaisán, J. Bilbao, Ind. Eng.
[3] M. Sugano, T. Tamaru, K. Hirano, K. Mashimo, Fuel 84 (2005) 2248. Chem. Res. 38 (1999) 4120.
[4] D.M. Money, G. Harrison, Fuel 78 (1999) 1729. [33] G. López, G. Elordi, M. Arabiourrutia, M. Olazar, R. Aguado, J. Bilbao,
[5] J.M. Lee, J.S. Lee, J.R. Kim, S.D. Kim, Energy 20 (1995) 969.
in: Proceedings of the Chemical Industry and Environment V, vol. II,
[6] A.M. Cunliffe, P.T. Williams, J. Anal. Appl. Pyrol. 44 (1998) 131. Viena, (2006), p. 970.
[7] P.T. Williams, A.J. Brindle, Fuel 83 (2003) 1023. [34] C. Di Blasi, Chem. Eng. Sci. 51 (1996) 1121.
[8] S. Ucara, S. Karagoza, A.R. Ozkanb, J. Yanikc, Fuel 84 (2005) 1884.
[35] H. Teng, M.A. Serio, M.A. Wojtowicz, R. Bassilakis, P.T. Solomon, Ind.
[9] C. Berrueco, E. Esperanza, F.J. Mastral, J. Ceamanos, P. Garcı́a-Bacaicoa, Eng. Chem. Res. 34 (1995) 3102.
J. Anal. Appl. Pyrol. 74 (2005) 245. [36] P.T. Williams, S. Bessler, Fuel 74 (1995) 1277.
[10] R. Murillo, M.V. Navarro, T. Garcı́a, J.M. López, M.S. Callén, E. Aylón, [37] D.Y.C. Leung, C.L. Wang, Energy Fuel 13 (1999) 421.
A.M. Mastral, Ind. Eng. Chem. Res. 44 (2005) 7228.
[38] J.F. González, J.M. Encinar, J.L. Canito, J.J. Rodrı́guez, J. Anal. Appl.
[11] S. Seidelt, M. Müller-Hagedorn, H. Bockhorn, J. Anal. Appl. Pyrol. 75 Pyrol. 58–59 (2001) 667.
(2006) 11.