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Applied Thermal Engineering 23 (2003) 1347–1358

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Coke deposition by physical condensation of


poly-cyclic hydrocarbons in the transfer line exchanger
(TLX) of olefin plant
H. Manafzadeh a, S.M. Sadrameli b,*
, J. Towfighi b

a
Khark Petrochemical Complex, Khark, Iran
b
Postgraduate School of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran
Received 10 December 2002; accepted 22 March 2003

Abstract
The formation and deposition of coke in industrial pyrolysis quenching system is a serious problem. There
are two mechanisms for the deposition of coke inside the exchanger tubes of naphtha crackers. In the first,
called chemical deposition, the coke formed by chemical reactions at the higher temperature region is de-
posited in the first half of the tubes. In the second half of the tubes, however because of the lower temperature
(T < 500 C), the coke deposition increases due to the physical condensation of heavy polycyclic hydro-
carbons. An accurate prediction of the exchanger parameters such as outlet temperature, pressure and coke
thickness inside the tubes is required for the ethylene plant operators. A comprehensive mathematical model
for a Transfer Line Exchanger (TLX) system in the industrial plant has been developed. The model in-
corporates a semi-empirical coke formation equation to predict a coke deposition rate both chemically and
physically and the effect of this coke on the TLX steady state and operational time performance. This paper
presents some of the results of the computer simulation for the naphtha pyrolysis quench cooler.
 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Coke deposition; Physical condensation; Fouling; Transfer line exchanger; Olefin plant

1. Introduction

The pyrolysis of hydrocarbon feedstocks involves two parallel reaction pathways. The primary
reactions lead to desirable products and the secondary reactions to undesirable products such as
methane and coke. This coke deposits on the walls of the reactor, reducing the overall heat

*
Corresponding author. Tel.: +98-911-276-5690; fax: +98-21-800-6544.
E-mail address: sadramel@modares.ac.ir (S.M. Sadrameli).

1359-4311/03/$ - see front matter  2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1359-4311(03)00088-7
1348 H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358

Nomenclature

A cross-sectional area of the tube, m2


Cp heat capacity, J/kmol K
D tube diameter, m
F molar flow rate, kmol/s
f Fanning friction factor
ff fouling factor, m2 K/W
G mass flux, kg/m2 s
h heat transfer coefficient, W/m2 K
L tube length, m
M molar mass, kg/kmol
nc total number of components
N total number of reactions
Nu Nusselt number
Pr Prandtl number
P pressure, kPa
Re Reynolds number
r rate of reaction, kmol/m2 s
T temperature, K
t time, s
U overall heat transfer coefficient, W/m2 K
z axial distance, m
Greek Letters
a coke lay-down factor
d coke thickness, m
DHR heat of reaction, J/kmol K
q gas density, kg/m3
l viscosity, Pa/s
Subscripts
c coke
o outside
w wall
z axial

transfer coefficient and increasing the pressure drop across the reactor. This results in both the
reactor tube metal temperature and the pressure drop across the reactor gradually increasing with
run time, leading to periodic shut downs. The purpose of the quench cooler unit or Transfer Line
Exchanger (TLX) is to quench and rapidly cool high temperature effluent from the cracking
furnace and to recover sensible heat from the cracked gas in the form of high pressure steam. The
formation of coke in the industrial pyrolysis furnaces is a severe problem. Coke deposits on the
H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358 1349

walls and elbows of the furnace tubes, in the transfer line exchanger, and on the inlet manifold and
tubes of the TLX. Multi-stream cracking coils are joined together into one by a collection
manifold to be led to a quench cooler through transfer line piping. Cracked gas normally at 780–
890 C is quenched and cooled to low temperature and, in exchange, generates high pressure
steam by recovering heat from the cracked gas. TLXs for ethylene cracking unit are mostly shell
and tube exchangers. A pyrolysis furnace and a quench cooler constitute a unit respectively. The
quench boiler inlet conditions are determined by the furnace outlet operation.
Typical exchanger inlet conditions are 780–890 C and 0.8–1.7 bar. For liquid feedstock such as
naphtha cracking, the exchanger outlet temperature must be high enough to avoid condensation
of heavy ends in the product gas (rapid fouling). For ethane/propane cracking the fouling of the
tubes by condensation of heavy components is small, but the tendency to plug the inlet tube sheet
by coke is normally the limiting factor. The circulation ratio (liquid/gas ratio) is defined as the
weight ratio of water over steam leaving the exchanger. Water circulation must always be
maintained to avoid stagnant water spaces in the shell (which causes steam blanketing) and to
decrease local concentration of salts (which may lead to overheating of tubes).
The fouling of quencher tubes increases, while heat transfer rate decreases with increase of
carbon deposit and eventually the fouling reaches an allowable maximum. Then, the furnace
operation has to be stopped to perform the carbon removal operation (decoking). Though both
furnaces and exchangers require occasional decoking, the intervals are usually different and the
operation of both furnace and quench cooler have to be stopped when either one of the two
reaches the coking limit, due to the fact that the two are directly connected by transfer line piping.
The reaction severity is defined as a ratio of ethylene to propylene in the reactor effluents. Op-
erating the furnace at higher severity leads to the higher coke formation and therefore lower
furnace run length. In mild or low severity cracking, the decoking interval of the quench cooler is
longer than that of the furnace (furnace limiting), whereas in high severity cracking, the coking
interval of quench cooler becomes shorter than the operation of pyrolysis furnace and the op-
eration of pyrolysis unit is usually quench cooler limiting.
Many different factors affect the coke deposition rate and the type of coke that deposits in the
pyrolysis coil and TLX tubes. The most important of these factors are the temperature, the tube
material and its surface roughness and the coke precursors such as acetylene and dienes in the
cracked gas. The formation of coke is thought to be occurred by three primary reaction mecha-
nisms of which only two are significant during the gas quenching operation in a TLX. The first
mechanism consists of surface catalysed reaction between pyrolysis-formed carbon and the me-
tallic tube wall to produce a filamentous coke containing metal particles. The second mechanism
of coke formation is the bulk gas polymerization of the pyrolysis products through undesirable
secondary reactions and the third mechanism is initiated by the local reactions between the gas
components with the active sites of the coke surface. The gas components in this case may be
acetylene, diolefins or methyl, vinyl and benzyl free radicals. These reactions result in the for-
mation of large chain polymers (poly-cyclic) and tars in the gas stream. Some of the heavier tars
and polymers condense on the pipe wall and react to produce a very smooth and hard coke. The
tars and polymers that do not condense may form a more amorphous coke in the gas phase that
subsequently deposits on the tube wall. Although many data on the nature of the deposited coke
have recently been reported, precise kinetic models of these various mechanisms especially in
the quench coolers for naphtha cracking have not been reported. Therefore in this work, coke
1350 H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358

formation rates given by existing naphtha cracking kinetics are tuned to industrial TLX operating
data (supplied by Arak Petrochemical Company (APC), Arak, Iran) by the introduction of two
empirical parameters, the coke thermal conductivity, kc and a coke lay-down factor (a).

2. Mathematical model

The mathematical model incorporates existing molecular kinetic data for predicting coke
formation rates in addition to the physical condensation of heavy poly-cyclic hydrocarbons, and a
semi-empirical coke deposition model for the thermal and hydrodynamic behaviour of the TLX.
Finally, the model is used to simulate the operating performance of an industrial TLX in the Arak
Petrochemical Complex and the results indicate a good match with full-scale plant operating data.
The model is based on the following simplifying assumptions:

• One dimensional plug flow model which implies the neglect of radial concentration gradients
and axial dispersion.

This assumption is valid for the conditions considered in this work [9].

• Constant outside tube wall temperature.

This is due to the fact that the latent heat in the shell side for the saturated water vaporization is
picked up from the cracked gas inside the exchanger tubes.

• Inertness of the steam in the feed.


• Horizontal and hydrodynamically smooth gas flow.
• Ideal gas behaviour for the cracked gas.
• No hydrodynamic or thermal entrance region effects.

A detailed discussion of the validity of these assumptions is given by Huntrods [2].


Given these assumptions, the following design equations can be written for the geometry of the
TLX.
The component mass balance equations for j ¼ 1; 2; nc components and i ¼ 1; 2; N reactions
are [3]
dFj XN
¼A sij ri j ¼ 1; 2; nc ð1Þ
dz i¼1
The energy balance equation becomes
P
dT A Ni¼1 ðDHRi ri Þ  U pDðT  Tw Þ
¼ Pnc ð2Þ
dz j¼1 Fj Cpj

And from the momentum balance,


dP 2fG2
¼ ð3Þ
dz Dq
H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358 1351

And finally, the inclusion of coke formation (coke thickness, dc ) is included by the coke deposition
model described later, which is of the general form,

dc ¼ dc ðz; tÞ ð4Þ

In this form, the model is pseudo-steady-state with respect to time. In other words, the solution
of Eqs. (1)–(3) is assumed constant over a time step, and the effects of coke formation through Eq.
(4) are updated explicitly at the end of each time step. This pseudo-steady-state assumption would
be indeed valid as long as coke formation rate does not change appreciably over a sufficiently
small time step. Nighswander et al. [7] showed that the quench time (actual gas residence time)
required to completely arrest propane pyrolysis reactions in a TLX tube is less than 20 ms. Eqs.
(1)–(4) are converted to a system of (j þ 3) simultaneous coupled initial value ordinary differential
equations. A detailed discussion of the terms and method of solution for these equations is
provided in following sections.

2.1. Kinetic model

Coke formation in the thermal cracking of hydrocarbons is a complex phenomenon [11] due to
the various possible coke forming free radical reactions and the exact mechanism is still not very
clear. Due to these uncertainties, only simple models involving either the reactant and/or products
were postulated. The carbon–stream reaction was not included in the models, because under these
conditions it is not expected to affect the coke deposition. The proposed models were shown that
coke can be formed either from the reactant, aromatics C6+, 1,3-butadiene, ethylene, and
propylene or from both C6+ and aromatics. The various models investigated are shown in Table
1. For each model, the asymptotic rate of coking was expressed in the power law form. The
parameters for the various models were determined by Kumar and Kunzru [5] using non-linear
optimization. The sum of squares of the deviations between the calculated and experimental
asymptotic coking rates was used as the objective function and minimized by the appropriate
choice of frequency factor, activation energy and reaction order. Model II was preferred over the
others because of the significantly lower residual SSQ. Thus, for model II, the expression for the
rate of coking can be written as

rc ¼ k3 ðCA Þn3 ¼ k3 expðE3 =RT ÞðFA PT =FT RT Þn3 ð5Þ

in which k3 ¼ 7:284  1013 and E3 ¼ 273:08  106 .


Neither of these models incorporates tube surface catalytic reactions, but it has been shown
by Fairburn [1] that these effects are negligible. The radical reaction scheme is expected to be
more accurate in describing the reaction kinetics, but it is also more complicated and time
consuming from a computational point of view. For propane pyrolysis quenching it was shown
by Nighswander et al. [7] that a molecular reaction scheme qualitatively predicts the same
kinetic behaviour as a far more complex radical reaction scheme with more than 80 reactions
that requires significantly more computational effort. As summarized by Kumar and Kunzru
[5], this reaction scheme consists of 22 reactions involving 14 molecular species and an inert
steam.
1352 H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358

Table 1
Various coke formation kinetic models
Model I
k1
Naphtha ! products
k2
Naphtha ! coke
Model II
k1
Naphtha ! products
k3
Aromatics ! coke
Model III
k1
Naphtha ! products
k4
C6+ ! coke
Model IV
k1
Naphtha ! products
k5
1,3-C4 H6 ! coke
Model V
k1
Naphtha ! products
k6
C2 H4 ! coke
Model VI
k1
Naphtha ! products
k7
C3 H6 ! coke
Model VII
k1
Naphtha ! products
k8
Aromatics ! coke
k9
C6+ ! coke

2.2. Heat transfer correlation

The overall heat transfer coefficient, U , in Eq. (2) is detailed based on the outside tube area as
follows:

1 Do ff i Do dc Do 1 xw Do
¼ þ þ þ þ þ ff o ð6Þ
U Di hi Di kc D ho kw D

The terms in Eq. (6) represent the inside fouling factor, the inside convective heat transfer re-
sistance, the resistance of the coke layer, the tube wall outside convective heat transfer resistance,
the wall conductive resistance, and the outside fouling factor, respectively. The numerical values
for the fouling factors are listed in Table 3. Radiation heat transfer, which was shown to have a
negligible contribution to the total heat flux, has been neglected in the equation. The coke thermal
conductivity, kc , is dependent on the type of coke formed and can be viewed as an adjustable
parameter. For the parametric studies to be presented later, a value of 2.2 W/m K for kc was used
for the base case calculations. The tube wall thermal conductivity, kw , is given by the following
expression [8]:

kw ¼ 24:4 þ 0:0041ðT  977:6Þ ð7Þ


H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358 1353

The inside convective heat transfer coefficient was calculated using the Dittus–Bolter equation as
follows:
0:8 0:33
ðNuÞz ¼ 0:023ðReÞz ðPrÞz ð8Þ
This equation does not take into account the heat transfer enhancement in the thermal entrance
region. It was shown by Nighswander et al. [7] that the entrance effects on the TLX are not large
and Eq. (8) provides a slightly conservative estimate of the heat transfer coefficient. The outside
heat transfer coefficient ho is large with respect to hi and as a result the last term in Eq. (6) can be
safely neglected. The calculation of the local Reynolds and Prandtl numbers requires the deter-
mination of the average gas transport properties. These were determined from the pure compo-
nent data with the application of mixing rules.
The Fanning friction factor in Eq. (3) was calculated from the following expression for smooth
pipes:
0:2
f ¼ 0:046NRe ð9Þ
Finally, the evaluation of heat of reaction (DHRi ) in Eq. (2), the standard heat of formation data
for the pure components were obtained from the literature [10].

2.3. Coke deposition

Coke is a complex of carbon and hydrogen. It may be formed either from the reactants and/or
from the products. Rate of coke formation depends on several factors, such as type of feed stock,
operating conditions, pyrolysis equipment, its material of construction and pre-treatment given to
the inner walls. The coke deposition model used in this work was derived from the basic coke
thickness equation of [6]. This equation represents the rate of coke thickness at a given axial
position:
 
ddc aMc rc
¼ ðDi  2dc Þ ð10Þ
dt 4qc
where a is the coke lay-down factor defined as the fraction of coke formed that deposits on the
tube wall, and rc is the rate of coke formation as predicted by the reaction kinetics. It should be
noted that the axial dependence of dc arises from the dependence of rc on temperature and thus z.
Integration of Eq. (10) yields
aMc rc
Ddc ¼ Dt ð11Þ
qc
Eq. (10) calculates the coke thickness change, dc over a time step Dt. This equation is solved at
each time step for the change in coke thickness at each axial position. This change was added to
update the total coke thickness for subsequent time steps.

2.4. Physical condensation

Due to the temperature variation in the TLX of naphtha crackers between 860 and 360 C, two
coke deposition mechanisms have the main role in the exchanger fouling. The first model which is
1354 H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358

30
25
20
15
10
5
0

ht H6
4

pe e

e
e
e

nt ne

hr e
2H
H

n
an
ap en
An len

le
ap C3
C
C2

e
ce
C

nt
s
M rac

ha
hy

y
ra

ht
th

lo
-A

yc
N
en

C
Ac
Fig. 1. Relative poly-aromatic hydrocarbons in TLX.

Table 2
Rates and dew points for the poly-cyclic hydrocarbons
Name Rate (mol/h) Dew point (C)
M-Anthracene 4.34 488
Acenaphthylene 9.54 317
Anthracene 5.64 381
Chrycene 7.56 380

basically chemical is dominated in the first half of the tube while the second model which is based
on the physical condensation is dominated in the remaining tube length. Kopinke et al. [4] in-
vestigated the second mechanism and concluded that the relative rate of coke deposition by
physical condensation is related to the rate of formation for poly-cyclic hydrocarbons in the
cracking gas. As shown in Fig. 1 the main components of coke deposited in the TLX are ace-
naphene, anthracene and chrysene. Therefore, due to the componentÕs dew point, listed in Table 2,
the coke will be deposited by condensation of heavy aromatics inside the tubes. This phenomenon
has been used to predict the thickness of coke deposited in the second half of the exchanger tubes.

3. Model solution

For the kinetic scheme, the model described by Eqs. (1)–(3) is actually an initial value problem
involving 32 simultaneous coupled ordinary differential equations. In addition, coke formation as
a function of operating time was incorporated through Eq. (4) by repeating the solution of Eqs.
(1)–(3) at every time interval. The solution to these equations was obtained by writing a computer
program using ‘‘C’’ language. The software may also be run in a personal computer.

4. Results and conclusions

The operating data for the industrial TLX were supplied by Arak Petrochemical Company
(APC), Arak, Iran. A summary of the exchanger TLX configuration and average feed compo-
sitions and conditions provided by APC is described in Tables 3 and 4. Average values of the feed
H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358 1355

Table 3
Operational data of an industrial TLX
Tube length 8.7 m
Tube ID 0.040 m
Tube thickness 0.008 m
Tubes number 130
Total exchanger area 70 m2
Steam temperature 325 C
Steam pressure 12 000 kPa
Cracked gas inlet temperature 866 C
Cracked gas inlet pressure 160 kPa
Cracked gas inlet velocity 100–120 m/s
Tube inside fouling factor, ffi 0.000688 m2 K/W
Tube outside fouling factor, ffo 0.000174 m2 K/W

Table 4
Inlet feed compositions
j Component mol%
1 Hydrogen 7.4
2 Carbon dioxide 0.003
3 Carbon monoxide 0.005
4 Hydrogen sulphide 0.015
5 Methane 14.1
6 Acetylene 0.43
7 Ethylene 16.26
8 Ethane 2.63
9 Propadiene 0.36
10 Propylene 3.94
11 Propane 0.156
12 Butadiene 0.97
13 C4 0.77
14 C5+ 2.5
15 H2 O 50.4

conditions were used since their actual day-to-day variation is quite small. The olefin plant is
consisted of eight naphtha cracking furnaces (seven in operation and one in decoking) each
connected to one TLX. Based on the input data listed in Tables 3 and 4, the simulation results of
the present work are shown in Figs. 2–6. Fig. 2 illustrates the predicted TLX temperature profiles
for the cracked gas inside the tubes of the exchanger. The data are shown for the three operation
time of the furnace i.e. start of run, SOR, middle of run, MOR, and end of run, EOR when the
maximum allowable exit temperature is reached and the exchanger is bypassed for decoking
operation. This temperature is about 440 C in the normal operation. The results are obtained for
a coke deposition factor of 0.225. As shown in Fig. 2, the coke deposition results in a decreased
rate of heat transfer causing the quench time steadily increase with operating time. The quench
time is defined as the actual time which the reaction kinetics predicts no appreciable further
1356 H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358

Temperature (C)
900

800

700

600 MOR

500 SOR EOR

400

300
0 20 40 60 80 100
Length, %

Fig. 2. Cracked gas temperature distribution inside the tubes.

Coke Thickness (mm)


12

10

E OR MOR
8

0
0 20 40 60 80 100
Length (%)

Fig. 3. Coke thickness in the tube at MOR and EOR.

reaction. The predicted coke thickness on the tubes of the exchanger for the MOR and EOR
operation times are shown in Fig. 3.
The coke deposited mainly in the second half of the tubes and concentrated at the tube outlet.
There are two main parameter to control the heat transfer in the TLX; the exit cracked gas
temperature and the outlet pressure inside the tubes.
Fig. 4 illustrates the predicted pressure profile inside the exchanger tubes at various operating
times, SOR, MOR and EOR. With the increased coke deposition, the tube pressure drop increases
sharply. The majority of this increase occurs at the tube entrance where the largest deposition of
coke is predicted. The results show that the maximum pressure drop inside the tubes will be 60
kPa at the end of operation time when the exchanger must be decoked. Having established a
match of the industrial data at Day 0 (start of run) the coke formation model was introduced to
predict the TLX outlet temperature after 63 days of operation. This was done by adjusting the
H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358 1357

Pressure (kPa)
160

SOR
150

MOR
140

130 EOR

120

110

100
0 20 40 60 80 100
Length (%)

Fig. 4. Cracked gas pressure distribution at SOR, MOR and EOR.

Outlet Temperature (c)


430

420

410

400

Experimental results, day 63


390

380

370
0.1 0.2 0.3 0.4 0.5
Coke lay down Factor

Fig. 5. Adjustment of coke lay-down factor by gas outlet temperature.

Pressure (kPa)
160

150 α = 0.125

α = 0.225
140

α = 0.425
130

120

110
0 20 40 60 80 100
Length (%)

Fig. 6. Adjustment of coke lay-down factor by gas outlet pressure.


1358 H. Manafzadeh et al. / Applied Thermal Engineering 23 (2003) 1347–1358

coke lay-down factor, a until an acceptable match of he Day 63 data provided by APC was
obtained. The predicted effect of a at Day 63 on the TLX outlet temperature is shown in Fig. 5. It
is observed from the figure that the predicted TLX outlet temperature is within 1 C of the in-
dustrial data for values of a between 0.20 and 0.23. Fig. 6 shows the effect of coke lay-down factor
on the pressure distribution inside the tubes. It is shown from the figure that the predicted outlet
pressure remains in the range provided by APC for values of a less than 0.3. In other words, it can
be concluded that a must be between 0.2 and 0.3 to much the industrial data. Therefore for this
particular exchanger an a of approximately 0.225 provides a good approximation of the TLX
operational time history.

5. Conclusions

A comprehensive model of a TLX tube in industrial gas quenchers has been developed. The
model incorporates a semi-empirical coke formation equation to predict a coke deposition rate
both chemically and physically and the effect of this coke on the TLX steady state and operational
time performance. The agreement between the results shows the accuracy of the mathematical
model. The model and simulation software presented here is used as a guide for plant operators in
APC to control the TLX.

Acknowledgements

The authors would like to thank Arak Petrochemical Company for providing the industrial
TLX data. The financial support from the National Petrochemical Company (NPC) is gratefully
acknowledged.

References

[1] J.A. Fairburn, Ultrapyrolysis of n-hexadecane in a Novel Micro-Reactor, M.Sc. Thesis, University of Calgary,
Alta., Canada, 1988.
[2] R.S. Huntrods, M. Eng. Thesis, University of Calgary, Calgary, Canada, 1988.
[3] R.S. Huntrods et al., Modeling of coke formation in gas quenchers of industrial ethane cracking furnace, Chem.
Eng. Res. Des. 67 (1989) 632–638.
[4] F.D. Kopinke, G. Bach, G. Zimmermann, New results about TLE fouling, J. Anal. Appl. Pyro. 27 (1993) 45–55.
[5] P. Kumar, D. Kunzru, Kinetics of coke deposition in naphtha pyrolysis, Can. J. Chem. Eng. 63 (1985) 598.
[6] I. Lichtenstein, Chem. Eng. Prog. 60 (12) (1964) 64.
[7] J.A. Nighswander, S.H. Richard, A.K. Mehrotra, L.A. Behie, Quench time modeling in Propane Ultra pyrolysis,
Can. J. Chem. Eng. 67 (1989) 608.
[8] H.F. Rase, Chemical Reactor Design for Process Plants, in: Case Studies and Design Data, vol. 2, John Wiley, New
York, 1977.
[9] K.M. Sundaram, G.F. Froment, Chem. Eng. Sci. 35 (1977) 601.
[10] J. Towfighi, A. Niaee, R. Karimzadeh, A kinetic model for the simulation of thermal cracking reactors in the olefin
plant, Iranian J. Sci. Tech. 55 (2) (1995) 68–75.
[11] J. Towfighi, M. Sadrameli, A. Niaei, Coke formation mechanisms and coke inhibiting methods in pyrolysis
furnaces, J. Chem. Eng. Jpn. 35 (10) (2002) 923–937.

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