The combined simulation of heat transfer

and pyrolysis reactions in industrial cracking furnaces
A. Niaei
b
, J. Towfighi
a
, S.M. Sadrameli
a,
*
, R. Karimzadeh
a
a
Chemical Engineering Department, Tarbiat Modarres University, P.O. Box 14115-143, Tehran, Iran
b
Department of Applied Chemistry, Tabriz University, Tabriz, Iran
Received 20 April 2003; accepted 28 January 2004
Available online 12 March 2004
Abstract
Thermal cracking of hydrocarbons for olefins production is carried out in large, gas fired furnaces
containing parallel reactor coils. The simulation of these coils requires detailed kinetics, based upon radical
reaction schemes and a rigorous description of heat transfer in the firebox. A complete modeling of the
reactor and the firebox, using a rigorous kinetic model, for the pyrolysis of naphtha has been developed and
is used here for the simulation of naphtha crackers. The coupled simulation of the reactor and the radiant
box by means of the zone method, results in the understanding of the behavior of the furnace. The sim-
ulation results are in good agreement with the experimental data. The model and computational scheme
can be used as a guide for plant operators and as a tool for design.
Ó 2004 Elsevier Ltd. All rights reserved.
Keywords: Simulation; Furnace; Firebox; Kinetic model; Thermal cracking
1. Introduction
The thermal cracking of hydrocarbons ranging from ethane to gas oil is the most important
source for the production of olefins and aromatics, the main feedstock of the petrochemical
industries. The hydrocarbon is diluted with steam (e.g., 0.3–0.4 kg steam/kg hydrocarbon in
ethane and propane cracking, and 0.6–0.7 for naphtha) to minimize undesired side reactions and
preheated to around 600–650 °C in the convection section of the furnace. The thermal cracking of
*
Corresponding author. Address: Department of Chemical Engineering, Chemical Engineering Building, University
of Florida, Gainesville, FL 32611-6005, USA. Tel.: +1-352-392-0226/98-21-8006544; fax: +98-21-8006544.
E-mail addresses: sadrameli@che.ufl.edu, sadramel@modares.ac.ir (S.M. Sadrameli).
1359-4311/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.applthermaleng.2004.01.016
Applied Thermal Engineering 24 (2004) 2251–2265
www.elsevier.com/locate/apthermeng
hydrocarbons is always accompanied by coke formation. The coke deposits on the walls of the
coil and affects the operation of pyrolysis coils with pressure drop increase, heat transfer reduc-
tion, hot spots and corrosion by carbonization. With the help of an accurate simulation of
pyrolysis reaction and radiant box of the industrial cracking furnaces one can then obtain a
favorable product distribution, prediction of the furnace run length or to reduce unwanted side
effects, such as coke deposition.
Hottel and Sarofim [1], and Paramenswaran et al. [2] simulated the firebox of the cracking
furnaces. Sadrameli [3] developed a mathematical model for the simulation of the naphtha
crackers using the multi-zone technique and assuming one dimensional conduction heat transfer
Nomenclature
A
i
area of a zone, m
2
C accumulation of coke, m
C
i
concentration of coke precursors, mole/m
3
C
p
heat capacity, J/mole K
d
t
tube diameter, m
E
i
black body emissive power, W/m
2
F molar flow rate, mole/h
G total mass flux of the process gas, kg/m
2
s
ÀDH heat of reaction, J/mole
k thermal conductivity of tube, W/m K
M
m
average molecular weight, kg/mole
n reaction order for coking
P
t
total pressure, kPa
Q heat flux, W/m
2
R
b
radius of the tube bend, m
r tube radius, m
r
c
coking reaction rate, kg/m
3
s
r
ri
reaction rate in pyrolysis process, mole/m
3
s
t
c
coke thickness, m
t time, h
s
ij
stochiometry factor
T temperature, K
Z
i
Z
j
total exchange area from zone i to j, m
2
Z axial reactor coordinate, m
Greek letters
a coking factor
K angle of bend 0
q
c
coke density, kg/m
3
g unit conversion factor
2252 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
in the reactor wall. This paper describes the results of a complete reaction network, using a
rigorous kinetic model, for the thermal cracking of the naphtha feed. The mathematical model for
the coke formation inside the reactor developed and is used for the simulation of naphtha crackers
[4]. The kinetic reaction network and coke formation model, are tested by the coupled simulation
of the reactor and the radiant box in an industrial cracking furnace. The model and computa-
tional scheme here can be used as a guide for plant operators and as a tool for design.
2. Mathematical models
2.1. Kinetic model
The reaction mechanism of thermal cracking of hydrocarbons is generally accepted as free-
radical chain reactions. A complete reaction network, using a rigorous kinetic model, for the
decomposition of the naphtha feed was developed, and is used for the simulation of a naphtha
cracker. The very detailed mechanistic kinetic scheme used in this simulation network, previously
developed by Towfighi and Nazari [5], Towfighi and Karimzadeh [6], involves over one thousand
reactions and 91 molecular and radical species. As usual this chain radical mechanism consists of
several radical and molecular elementary reactions.
Some kinetic extensions were made and the kinetic parameters were verified and tuned with a
large amount of pilot plant and industrial data. Some of the experiments are described and their
results are compared with those obtained from model. Finally a complete reaction network was
obtained for the decomposition of naphtha feed. Typical reactions of the kinetic model for
thermal cracking of naphtha are listed in Table 1.
The governing mass, energy, and momentum balance equations for the cracking coils constitute
the boundary value problem which has a significant stiffness in the numerical simulation due to
the large differences in concentration gradient between radicals and molecules. This problem can
be tackled through the application of the Gear method.
2.2. Coking model
A number of coke precursors are contributed in the formation of coke. Unsaturated hydro-
carbons and aromatics are a very important class of coke precursors. They are products of the
pyrolysis reactions so that their concentration in the high temperature zone of the reactor is high.
Unsaturated components are reactive and are good candidates for the radical addition. Also
aromatic ring structure is close to the structure of the coke matrix. Further, (branched) aromatics
are reactive components, especially at the high temperatures prevailing in thermal cracking coils.
The literature survey and plant data led to a coking model in which a number of coke precursors
and the relative rates of coke deposition contribute to the formation of coke [7–9]. The precursors
are classified into different groups, such as olefinic (ethylene, propylene, 1-butene), acetylenic
(acetylene, methyl acetylene, ethyl acetylene, vinyl acetylene), aromatics (benzene, toluene, xylene,
styrene), C5+ (unsaturated). The residual sum of squares between the calculated values and
asymptotic coking rates (literature and plant observations) was used as the objective function and
A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265 2253
the coking kinetic parameters were estimated by using the Marquardt algorithm. The following
expression can then be written for coke formation rate of contributed precursors:
r
c
¼ k
olefins
C
n1
olefins
þk
Actylenic
C
n2
Actylenic
þk
Aromatics
C
n3
Aromatics
þk
C5þ
C
n4
C5þ
ð1Þ
where k
i
in Eq. (1) is the rate constant of coke formation reactions. The coke formation takes
place at the temperature of the gas/coke interface [7].
2.3. Reactor model
A one-dimensional plug flow model is used to simulate the thermal cracking reactor. The set of
continuity equations for the various process gas species is solved simultaneously with the energy,
momentum and the coking rate equations required [10]. These equations are as follows:
Mass balance:
dF
j
dz
¼

i
s
ij
r
ri
_ _
pd
2
t
4
ð2Þ
Energy balance:

j
F
j
c
pj
dT
dz
QðzÞpd
t
þ
pd
2
t
4

i
r
ri
ðÀDHÞ
i
ð3Þ
Table 1
Typical reactions of the model for thermal cracking of naphtha
(A) Radical reactions
(1) Initiation reactions
Unimolecular: CH
3
–CH
2
–CH
2
–CH
2
–CH
3
fiC
3
H
Å
7
+C
2
H
Å
5
Bimolecular: CH
3
–CH
3
+CH
2
@CH
2
fiC
2
H
Å
5
+C
2
H
Å
5
(2) Propagation reactions
Radical decomposition: CH
Å
2
–CH
2
–CH
3
fiC
2
H
4
+CH
Å
3
Radical isomerization: CH
Å
2
–CH
2
–CH
2
–CH
2
–CH
3
fiCH
3
–CH
2
–CH
2
–CH
Å
–CH
3
H-abstraction on molecules: CH
Å
3
+CH
3
–CH
3
fiCH
4
+C
2
H
Å
5
Addition of radicals on unsaturated molecules: CH
Å
3
+CH
2
@CH
2
fiCH
3
–CH
2
– CH
Å
2
(3) Termination reactions
Recombination of radicals to form a molecule: CH
Å
3
+CH
Å
3
fiCH
3
–CH
3
C
2
H
Å
5
+C
2
H
Å
5
fiCH
3
–CH
3
+CH
2
@CH
2
(B) Molecular reactions
Olefin isomerization: CH
3
–CH@CH–CH
3
fiCH
2
@CH–CH
2
–CH
3
Olefin dehydrogenation: CH
2
@CH–CH
2
–CH
3
fiCH
2
@CH–CH@CH
2
+H
2
Olefin decomposition: CH
2
@CH–CH
2
–CH
2
–CH
3
fiCH
2
¼CH–CH
3
+CH
2
@CH
2
Diels-Alder reaction: CH
2
@CH–CH@CH
2
+CH
2
@CH
2
fiCyclo C
6
H
10
2254 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
Momentum balance:
1
M
m
P
t
_
À
P
t
g Á G
2
RT
_
dp
t
dz
¼
d
dz
1
M
m
_ _
þ
1
M
m
1
T
dT
dz
_
þ Fr
_
ð4Þ
with the friction factor:
Fr ¼ 0:092
Re
À0:2
d
t
þ
f
pR
b
ð5Þ
and for the tube bends as:
f ¼ 0:7
_
þ0:35
K
90
0
_
0:051
_
þ0:19
d
t
R
b
_
ð6Þ
where R
b
and K represent the tube bend radius and bed angle respectively. Since the coking is
slow, quasi steady state conditions may be assumed, so that, we can write the rate of coke for-
mation:
oC
ot
¼ ðd
t
À2t
c
Þ
ar
c
q
c
ð7Þ
Using the mathematical model, the amount of coke deposited on the internal wall of the reactor
tubes can be calculated with a limiting value for tube skin temperature (1100 °C).
2.4. Heat transfer model
The configuration of the cracking coil inside the furnace, the positioning and type of the
burners require special attention. With the help of an accurate simulation for the radiative heat
exchange in a furnace the calculation of the temperature and heat flux distributions in the firebox
and the reactor can be achieved. The multizone mathematical model and the three-dimensional
model has been applied to simulate the thermal cracking furnaces of Arak Olefin Plant [3]. The
furnace refractory walls, the surface reactor coils and the flue gas volume were discretized into a
number of isothermal surface and volume zones with uniform properties. For the calculation of
the direct and total-exchange areas, a fundamental approach considering individual band
absorption by carbon dioxide and water, are taken. In addition, the position of the burners in the
furnace walls and the flue gas flow pattern in the firebox are explicitly accounted for. Zone method
involves subdivision of the radiating enclosure into isothermal volume and surface zones.
Mathematical models based on the zone method vary in complexity, depending on the number
and arrangement of zones.
The multi-dimensional zone model is used when both longitudinal and cross sectional or radial
variation in temperature and heat flux are expected to be important. In this model the furnace
refractory walls, the tubes and the furnace volume are divided into a number of isothermal surface
and volume elements with uniform properties. The energy balance, containing the contribution of
radiative, convective and/or conductive heat exchange, is constructed for each element, resulting
in a set of non-linear algebraic equations in the form:
A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265 2255
Z
1
Z
1
À

Z
i
Z
j
. . . :Z
2
Z
1
. . . . . . . . . . . . . . . . . . Z
n
Z
1
. . . . . . Z
1
Z
2
. . . . . . Z
2
Z
2
À

Z
2
Z
2
. . . . . . . . . Z
n
Z
2
. . . . . .
. . . . . .
. . . . . .
. . . . . . Z
1
Z
n
. . . . . . Z
2
Z
n
. . . . . . . . . Z
n
Z
n
À

Z
n
Z
j
_
¸
¸
¸
¸
¸
¸
_
_
¸
¸
¸
¸
¸
¸
_
Á
E
1
E
2
. . .
. . .
. . .
E
n
_
¸
¸
¸
¸
¸
¸
_
_
¸
¸
¸
¸
¸
¸
_
¼
Q
1
A
1
Q
2
A
2
. . .
. . .
. . .
Q
n
A
n
_
¸
¸
¸
¸
¸
¸
_
_
¸
¸
¸
¸
¸
¸
_
ð8Þ
The matrix element Z
i
Z
j
represents the total exchange area between the zone Z
i
and Z
j
. This is the
amount of radiative energy emitted by the zone Z
i
and absorbed, both directly and after reflection
on other zones, by the zone Z
j
, divided by the black body emissive power E
i
. The emissive of a
black body with temperature T
i
is given by Stefan–Boltsmann law. The non-radiative heat flux
emitted by zone Z
i
is represented by Q
i
. Solving the set of energy balances yields the heat flux and
temperature distribution in the furnace. When the reactor tubes are discretized in axial direction
only, heat flux profiles qðzÞ and external tube skin temperature profiles T
ext
ðzÞ are obtained. When
the tubes are also discretized along the perimeter, three-dimensional temperature profiles Tðr; h; zÞ
are obtained using the following equation for each axial tube zone:
1
r
o
or
kr
oT
or
_ _
þ
1
r
2
o
oh
k
oT
oh
_ _
þ
o
oz
k
oT
oz
_ _
¼ qC
p
oT
ot
ð9Þ
Assuming that the temperature in each small element is constant, Eq. (9) can be simplified as:
r
2
T ¼
o
2
T
or
2
þ
1
r
oT
or
þ
1
r
2
o
2
T
oh
2
¼ 0 ð10Þ
The discretization and solution of the above equation along with the boundary conditions have
been discussed in detail by Heynderickx et al. [11].
3. Experimental setup
The pyrolysis experiments have been conducted in a pilot plant system, which was designed and
assembled, for studying of the pyrolysis reaction kinetics. The setup is a computer controlled pilot
plant unit [7] as shown in Fig. 1. The hydrocarbon and diluent water are heated up 600 °C in
preheaters. The reactor heater is divided into eight zones, which can be heated independently to
control the temperature profile. The power for each zone can be controlled by a control algorithm
implemented on the process computer. The reactor is a 1 m long, 10 mm internal diameter tube,
made of Inconel 600. There are eighteen thermocouples along the reactor; eight inside the furnace;
eight on the external tube skin and additional two for measuring of XOT (cross-over temperature)
and COT (coil outlet temperature). The reactor is heated electrically and placed vertically in a
cylindrical furnace.
The analog signals of the thermocouples are connected to the process computer. The reactor
effluent is cooled and separated by means of three condensers and cyclones. A fraction of the
product gas is then withdrawn for the analysis, while the rest is sent to the flare. The on-line
analysis of the reactor effluent is performed by means of two computerized Varian Chrompack
CP3800 gas chromatographs, which analyses the cracked gases and condensate.
2256 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
A PIII process computer is connected on-line to the pilot plant and controls the main part of
the unit. The connection with the pilot plant is done through the analog to digital (A/D), digital to
analog (D/A) converters, and digital input–outputs. In control part of the furnace, the temper-
ature profile of the reactor is stabilized by temperature controlling in each zone by means of a
conventional PID controller. The set points for this temperature stabilizing control are included in
the software. All pilot plant measurements and control system information are saved in the text
and graphical mode.
The experiments were conducted at atmospheric pressure in the coil outlet temperature range of
800–870 °C. The dilution steam ratio was in the range of 0.6–0.8 and the residence time was varied
from 0.2–0.5 s. The preheating temperature range was 580–600 °C. The feedstock was straight run
LIQUID
FEED
BALANCE
PUMP
TT TT
TT TT
WATER
BALANCE
PUMP
TT
TT
WATER
PRE HEA TER
FEED
PRE HEA TER
C
E
N
A
U
R
F
N
E
Z
O
8
E
X
C
H
A
N
G
E
R
EXCHANGER
WATER
CONDENSATE
H.C.
CONDENSATE
GAS
COUNTOR
GASEOUS FEED
VENT
AIR FILTER
COMPRESSOR
AIR FOR DECOKING
TT
TT
TT
TT
TT
TT
TT
TT
TT
TT
TT
TT
G.C.
FLARE
8
7
6
5
4
3
2
1
1
2
3
4
6
7
8
5
INTERFAC
E CARD
INPUT
SIGNALS
OUTPUT
SIGNALS
TT
Fig. 1. Schematic diagram of the thermal cracking setup.
A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265 2257
naphtha obtained from Arak Petrochemical Complex with the same composition used in the plant
as listed in Table 2.
4. Simulation procedure and results
Coupling the reactor model and radiant box simulation requires the simultaneous solution of
the rigorous kinetic model for the pyrolysis of naphtha, coking model and energy balance
equations for the firebox. The run time is increased in a stepwise manner. Incremental pseudo
steady state is assumed for the coking, since the main cracking reactions are much faster than the
coke formation. Starting from the initial estimates for the temperature, heat flux and recycle gas
composition, the energy balance, Eqs. (8) and (10) are solved and better estimates for the zone
temperatures provided. From the tube skin and process gas temperatures, new flux estimates are
then calculated.
Based on the new fluxes, the process gas and recycled gas composition, temperature, and
pressure are calculated from Eqs. (2)–(4). By solving Eq. (10), new zone temperatures are obtained
which are compared to the previously obtained values. The cycle is repeated until convergence is
reached for the time increment. For the present simulation program, run time increment of 50 h
was found to be significant. For each time increment, a coupled furnace and reactor simulation is
performed.
The furnace contains eight split reactor coils in a staggered row configuration. Table 3 repre-
sents the reactor configuration, material properties and the feedstock compositions of the
industrial cracking furnace. Table 4 lists the characteristics of the industrial naphtha cracking
furnace, fuel and flue gas conditions. Figs. 2 and 3 show the coil configurations, and top and front
views of the burners on the rear walls of the furnace. The burners (108) positioned on the
refractory walls, provide the required heat flux for the reactor. The furnace is divided into zones
by means of four equidistant horizontal planes. Coil outlet temperature, feed conditions, and run
length or maximum tube skin temperature are the main parameters, which can be altered in the
model. The external tube skin temperature is measured periodically by the radiation pyrometers,
through the peepholes located on the furnace walls. The simulated results show that the observed
Table 2
Specification of naphtha feed
Naphtha composition (wt%)
n-Butane 4.53 2,2,3-Trimethylbutane 7.20
iso-Butane 0.12 Benzene 2.17
n-Pentane 22.52 Toluene 0.37
iso-Pentane 16.48 p,m-Xylene 0.44
2,2-Dimethylbutane 0.30 Cyclohexane 7.112
2,3-Dimethylbutane 1.18 n-Heptane 1.69
Cyclopentane 7.38 2,3-Dimethylpentane 1.10
2-Methylpentane 12.17 n-Octane 0.63
n-Hexane 12.02 iso-Octane 0.20
2,4-Dimethylpentane 2.30 n-Nonane 0.07
2258 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
temperatures depend upon the location of the peephole with respect to the tubes. The results of
the model have been compared with the design data obtained from the plant. Unfortunately
except for the tube skin temperature, which is measured by the pyrometer, other characteristics of
Table 3
Basic information of cracking coils
Reactor configuration
Total reactor length (m) 45
I. D./O. D. (mm) (for the first pass 0–22.5 m) 85/92
I. D./O. D. (mm) (for the second pass 22.5–45 m) 121/130
Material properties
Tube thermal conductivity (W/mK) )1.257 +0.0432 T
Coke thermal conductivity (W/mK) 6.46
Coke spgr (kg/m
3
) 1680
Feed characteristics
n-Paraffins 41.43
i-Paraffins 41.02
Naphthenes 14.05
Aromatics 2.98
Table 4
Basic information of radiant box
Furnace characteristics
Height (m) 11.473
Length (m) 10.488
Depth (m) 2.1
No. of burners 108
No. of end wall zones 22
No. of roof zones 4
No. of bottom zones 4
No. of cold plane zones 44
No. of gas cube zones 44
Zone dimensions (m) 1.05
Fuel composition (wt%)
H
2
14
CH
4
86
Excess air 15
Flue gas composition (wt%)
CO
2
12.72
H
2
O 12.96
O
2
2.88
N
2
71.44
Flue (mole flue/mole fuel) 10.902
A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265 2259
the coils such as coke thickness measurement are not possible during the operation. The com-
parison with the industrial plant data is made only for the tube skin temperature results and other
parameters are based on the design data. The evolution of the maximum tube skin temperature
should be watched carefully during operation, since there is a temperature limit imposed by the
tube metallurgy. In the present case study the limiting value was taken as 1100 °C and it is reached
after 70 days (simulated) of operation. The simulated data is in agreement with the observed plant
value, which was 73 days.
Fig. 4 shows the main product yields over the length of the reactor. The feed flow rates were
kept constant over the run length and good agreement is observed between these results especially
for the main product yields. In general, with an increase in conversion, the yield of propylene
increases, reaches to the maximum at the middle of the reactor and then decreases. The thermally
Downflow
Upflow
Burner
Fig. 2. Top view of the naphtha cracking coils.
Fig. 3. Front view of the naphtha-cracking furnace.
2260 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
stable products such as methane, ethylene and aromatic components will also be increased.
Aromatics were also formed by reaction between the cracking products of olefins and diolefins.
The growth of the coke layer and the amount of heat transferred to the reacting process gas and
pressure level are the main factors, which affect the product yields and selectivity.
Fig. 5 illustrates the simulated thickness of the coke layer as a function of run length. The run
time (the case study of this paper) is 1700 h (70 days). At the same plant operating and simulation
conditions, the run time remains constant. The coke deposition are higher on the surface of U-
shapes (bending area) and reaches its maximum in the last pass at the length of 42 m, corre-
sponding to a reduction in diameter of about 14%. At the tube length of 22 m where is the split
part of the reactor, the coke layer is less important (Sudden expansion of coil from 81 to 121 mm
0
5
10
15
20
25
30
35
0 5 10 15 20 25 30 35 40 45
Reactor Length (m)
Y
i
e
l
d

(
w
t
%
)
C
2
H
4
C
4
H
6
Aromatics
CH
4
C
3
H
6
Fig. 4. Profile of main product yields along the coil.
0
2
4
6
8
10
12
14
0 5 10 15 20 25 30 35 40 45
Reactor Length (m)
C
o
k
e

t
h
i
c
k
n
e
s
s

(
m
m
)

800 hr
1700 hr
1200 hr
Fig. 5. Variation of coke thickness along the coil at different run length.
A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265 2261
internal diameter). This is also shown in Fig. 5. Therefore, due to the low coking rate or low coke
thickness in split part, the heat flux will have a lower value. The coke formation takes place at the
temperature of the gas/coke interface. Since there is no experimental data for the coke thickness,
the comparison can only be made by the pressure drop measurement in the reactor as shown in
Table 5. However, the coking rates are high in the second part of the reactor so that the con-
centration of coke precursors in the high temperature zone of the reactor is high. As a conse-
quence, the coke layer grows fast there and creates an additional resistance to heat transfer and
causes a decrease on the tube cross-sectional area.
Fig. 6 shows the variation of the heat flux as a function of time. The high heat flux in the first
part of the reactor is resulted from the higher conversion requirement, to achieve the constant
ethylene yield, in spite of the increase in the reactor pressure. It compensates for the decrease of
the heat flux in the second part of the reactor caused by the coke formation. The heat flux de-
creases sharply at a reactor length of 22 m since at this point the reactor diameter is increased. The
heat flux then increases to compensate for the required heat of reaction. Fig. 7 shows the variation
of the external wall, internal wall, coke surface, and process gas temperature profiles along the
cracking coils. In the first part of the reactor, the temperature profile shows a significant increase,
but this is mainly due to the higher heat flux. The peaks on the external and internal tube skin
temperature profiles correspond to the bottom of the furnace where the reactor experiences the
higher heat flux from the burners. The maximum value is reached at the end of the second pass.
The formation and deposition of coke on the inner surface of the coil has major consequences on
the operation of the furnace. The coke layer reduces the heat transfer from the furnace to the
process gas. The process gas temperature is relatively insensitive to the heat flux variations. This is
Table 5
Comparison of the simulation results
Yields (%) Simulation results Plant data Pilot plant
H
2
1.00 1.2 1.44
CH
4
17.07 17.7 18.4
C
2
H
2
1.16 0.93 1.4
C
2
H
4
35.14 35.42 35.0
C
2
H
6
6.07 6.04 6.0
C
3
H
6
12.53 12.05 12.2
C
3
H
8
0.43 0.48 0.4
C
4
H
6
4.52 4.23 4.5
C
4
H
8
1.47 1.8 2.5
C
4
H
10
0.36 0.24 0.3
Aromatics 11.0 10.82 12.1
Others 9.23 9.09 5.67
Operating conditions
H.C. flow rate (kg/h) 11600 11600 0.4
COT (°C) 860 860 870
Coil outlet pressure 1.6 1.55 1
Coil inlet pressure 2.2 2.2 –
Steam ratio 0.7 0.7 0.7
Residence time (s) 0.4 0.4 0.6
2262 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
due to the very high mass flow rate of the process gas in the reactor, which dampens changes in
heat input. This is also affected by the endothermic nature of the pyrolysis reactions that has a
self-stabilizing effect on the process gas temperature. Fig. 8 shows the refractory and flue gas
temperature profiles inside the firebox. These values are normally measured by the pyrometer
from the outside wall of the furnace. Fig. 9 shows the comparison between the simulated and
plant data for the main products yield such as ethylene, propylene, butadiene and aromatic over
the run time of the reactor. The feed flow rates were also kept constant over the run length. The
growth of the coke layer, the amount of heat transferred to the gas and pressure are factors, which
affect the ethylene yield. The simulation results and plant data are in close agreement. Table 5
shows the comparison between the simulated results and plant data. The calculated product
yields, coil outlet temperature and pressure results match with the plant data with acceptable
accuracy. The accuracy of the kinetic reaction scheme was tested by the experimental results of the
pilot plant. For different operating conditions the calculated results are in good agreement with
and experimental data, as typically presented in this table.
10
15
20
0 10 20 30 40
Reactor Length (m)
H
e
a
t

f
l
u
x

(
k
c
a
l
/
m
2
s
)
0 hr
800 hr
1700 hr
Fig. 6. Variation of heat flux on the length of reactor.
600
700
800
900
1000
1100
1200
0 5 10 15 20 25 30 35 40 45
Reactor Length (m)
T
e
m
p
e
r
a
t
u
r
e

(
°
C
)
Tg
Tc
Tw
Two
Fig. 7. Temperature profiles of the firebox and the reactor.
A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265 2263
5. Conclusions
With the help of an accurate simulation of pyrolysis reactor and radiant box in a cracking
furnace, the distribution of the temperature and heat flux in the reactor and firebox can be pre-
dicted. Experimental data from the pilot plant system and plant information were combined to
obtain a kinetic model for the coke formation in thermal cracking. This coking model was
combined with a rigorous kinetic model for the cracking reactions, to simulate the run length of a
furnace for the thermal cracking of naphtha. The simulated and plant observation run length data
are very close together with acceptable accuracy. Simulations of this kind can be used to design
and optimize the furnace operation for various feedstock compositions, firing and operating
conditions. The results can be used as a guide for the plant operators and as a tool for the
designers.
0
2
4
6
8
10
12
700 800 900 1000 1100 1200 1300
Temperature (°C)
H
e
i
g
h
t

(
m
)
T (flue gas)
T (Refractory)
Fig. 8. Flue gas and refractory temperature profiles vs. furnace height.
0
5
10
15
20
25
30
35
40
0 300 600 900 1200 1500 1800
Run time (hr)
Y
i
e
l
d
s

(
%
w
t
)
C
2
H
4
C
3
H
6
Aromatics
C
4
H
6
Solid lines: Simulation
Points: industrial data
Fig. 9. Comparison of the simulation and industrial results for the main product yields.
2264 A. Niaei et al. / Applied Thermal Engineering 24 (2004) 2251–2265
Acknowledgements
The information support provided by Olefin plant of Arak Petrochemical Company, APC, is
gratefully acknowledged.
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