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Applied Thermal Engineering xxx (2003) xxx–xxx

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2 Coke deposition by physical condensation of

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3 poly-cyclic hydrocarbons in the transfer line exchanger
4 (TLX) of olefin plant

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5 H. Manafzadeh b, S.M. Sadrameli a,*
, J. Towfighi a

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

9 Abstract
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10 The formation and deposition of coke in industrial pyrolysis quenching operation is a serious problem.
11 Ethylene plant operators require a prediction for the exchanger parameters such as outlet temperature and
12 pressure and also the coke thickness inside the exchanger tubes. There are two mechanisms for the de-
13 position of coke inside the exchanger tubes. In the first, called chemical deposition, the coke formed by
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14 chemical reactions at the higher temperature region is deposited in the first half of the tubes. In the second
15 half of the tube, however due to the lower temperature (T < 500
C) the coke deposition increases due to
16 the physical condensation of heavy poly-cyclic hydrocarbons. This paper presents some of the results of a
17 rigorous computer simulation for a naphtha pyrolysis quench cooler or transfer line exchanger (TLX).
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18  2003 Published by Elsevier Science Ltd.

19 Keywords: Coke deposition; Physical condensation; Fouling; Transfer line exchanger; Olefin plant
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20 1. Introduction

21 The pyrolysis of hydrocarbon feedstocks involves two parallel reaction pathways. The primary
22 reactions lead to desirable products and the secondary reactions to undesirable products such as
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23 methane and coke. This coke deposits on the walls of the reactor, reducing the overall heat
24 transfer coefficient and increasing the pressure drop across the reactor. This results in both the
25 reactor tube metal temperature and the pressure drop across the reactor gradually increasing with

*
Corresponding author. Tel.: +98-21-801-1011; fax: +98-21-800-6544.
E-mail address: sadramel@modares.ac.ir (S.M. Sadrameli).

1359-4311/03/$ - see front matter  2003 Published by Elsevier Science Ltd.

doi:10.1016/S1359-4311(03)00088-7
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2 H. Manafzadeh et al. / Applied Thermal Engineering xxx (2003) xxx–xxx

Nomenclature

A cross-sectional area of the tube, m2

Cp heat capacity, J/kmole K
D tube diameter, m

F
F molar flow rate, kmole/s
f Fanning friction factor

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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/kmole

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nc total number of components
N total number of reactions
Nu Nusselt number
Pr Prandtl number
P pressure, kPa
Re
r
T
Reynolds number
rate of reaction, kmole/m2 s
temperature, K
D
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t time, s
U overall heat transfer coefficient, W/m2 K
z axial distance, m
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Greek Letters
a coke lay-down factor
d coke thickness, m
DHR heat of reaction, J/kmole K
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q gas density, kg/m3

l viscosity, Pa/s
Subscripts
c coke
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o outside
w wall
z axial
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26 run time, leading to periodic shut downs. The purpose of the quench cooler unit or Transfer Line
27 Exchanger (TLX) is to quench and rapidly cool high temperature effluent from cracking furnace
28 and to recover sensible heat of the cracked gas in the form of high pressure steam. The formation
29 of coke in the industrial pyrolysis furnaces is a severe problem. Coke deposits on the walls and
30 elbows of the furnace tubes, in the transfer line exchanger, and on the inlet manifold and tubes of
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31 the TLX. Multi-stream cracking coils are joined together into one by a collection manifold to be
32 led to a quench cooler through transfer line piping. Cracked gas which normally is at 820–840
C
33 is quenched and cooled to low temperature and, in exchange, generates high pressure steam by
34 recovering sensible heat to the cracked gas. TLXs for ethylene cracking unit are mostly shell and
35 tube exchangers. A pyrolysis furnace and a quench cooler constitute a unit respectively. The
36 quench boiler inlet conditions are determined by the furnace outlet operation.

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37 Typical inlet conditions are 780–860
C and 0.8–1.7 bar. For liquid feedstock such as naphtha
38 cracking, the exchanger outlet temperature must be high enough to avoid condensation of heavy

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39 ends in the product gas (rapid fouling). For ethane/propane cracking the fouling of the tubes by
40 condensation of heavy components is small, but the tendency to plug the inlet tube sheet by coke
41 is normally the limiting factor. The circulation ratio (liquid/gas ratio) is defined as the weight ratio
42 of water over stream leaving the boiler. Water circulation must always be maintained to avoid
stagnant water spaces in the shell (which causes steam blanketing) and to avoid local concen-

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43
44 tration of salts (which may lead to overheating of tubes).
45 The fouling of quencher tubes increases, while heat transfer rate decreases with increase of
46 carbon deposit and eventually the fouling reaches an allowable maximum. Then, the furnace
47 operation has to be stopped to perform a carbon removal operation (decoking). Though both
48 furnaces and exchangers require occasional decoking, the intervals are usually different and the
49
50
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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.
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51 The reaction severity is defined as a ratio of ethylene to propylene in the reactor effluents. Op-
52 erating the furnace at higher severity leads to the higher coke formation and therefore lower
53 furnace run length. In mild or low severity cracking, the decoking interval of the quench cooler is
54 longer than that of the furnace (furnace limiting), whereas in high severity cracking, the coking
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55 interval of quench cooler becomes shorter than the operation of pyrolysis furnace and the op-
56 eration of pyrolysis unit is usually quench cooler limiting.
57 Many different factors affect the coke deposition rate and the type of coke that deposits in the
58 pyrolysis coil and TLX tubes. The most important of these factors are the temperature, the tube
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59 material and its surface roughness and the coke precursors such as acetylene and dienes in the
60 cracked gas. The formation of coke is thought to occur by three primary reaction mechanisms of
61 which only two are significant during the gas quenching operation in a TLX. The first mechanism
62 consists of surface catalysed reaction between pyrolysis-formed carbon and the metallic tube wall
63 to produce a filamentous coke containing metal particles. The second mechanism of coke for-
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64 mation is the bulk gas polymerization of the pyrolysis products through undesirable secondary
65 reactions and the third mechanism is initiated by the local reactions between the gas components
66 with the active sites of the coke surface. The gas components in this case may be acetylene, di-
67 olefins or methyl, vinyl and benzyl free radicals. These reactions result in the formation of large
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68 chain polymers (poly-cyclic) and tars in the gas stream. Some of the heavier tars and polymers
69 condense on the pipe wall and react to produce a very smooth and hard coke. The tars and
70 polymers that do not condense may form a more amorphous coke in the gas phase that subse-
71 quently deposits on the tube wall. Although many data on the nature of the deposited coke have
72 recently been reported, precise kinetic models of these various mechanisms especially in the
73 quench cooler for naphtha cracking have not been reported. Therefore in this work, coke for-
74 mation rates given by existing naphtha cracking kinetics are tuned to industrial TLX operating
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75 data (supplied by Arak Petrochemical Company (APC), Arak, Iran) by the introduction of two
76 empirical parameters, the coke thermal conductivity, kc and a coke lay-down factor (a).

77 2. Mathematical model

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78 The mathematical model incorporates existing molecular kinetic data for predicting coke for-
79 mation rates in addition to the physical condensation of heavy poly-cyclic hydrocarbons, and a

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80 semi-empirical coke deposition model for the thermal and hydrodynamic behaviour of the TLX.
81 Finally, the model is used to simulate the operating performance of an industrial TLX in the Arak
82 Petrochemical Complex and the results indicate a good match with full-scale plant operating data.
83 The model is based on the following simplifying assumptions:

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

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

87 • Constant outside tube wall temperature D

This is due to the fact that the latent heat in the shell side for the saturated water vaporization is
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88
89 picked up from the cracked gas inside the exchanger tubes.

90 • Inertness of the steam in the feed

91 • Horizontal and hydrodynamically smooth gas flow
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92 • Ideal gas behaviour for the cracked gas

93 • No hydrodynamic or thermal entrance region effects

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

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95 Given these assumptions, the following design equations can be written for the geometry of the
96 TLX.
97 The component mass balance equations for j ¼ 1; 2; nc components and i ¼ 1; 2; N reactions are
98 [3]
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dFj XN
¼A sij ri j ¼ 1; 2; nc ð1Þ
dz i¼1

100 The energy balance equation becomes

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PN
dT A j¼1 ðDHRi ri Þ  UpDðT  Tw Þ
¼ Pnc ð2Þ
dz j¼1 Fj Cpj

102 And from the momentum balance,

dP 2fG2
¼ ð3Þ
dz Dq
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104 And finally, the inclusion of coke formation (coke thickness, tc ) is included by the coke deposition
105 model described later, which is of the general form,
dc ¼ dc ðz; tÞ ð4Þ
107 In this form, the model is pseudo-steady-state with respect to time. In other words, the solution
108 of Eqs. (1)–(3) is assumed constant over a time step, and the effects of coke formation through Eq.

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109 (4) are updated explicitly at the end of each time step. This pseudo-steady-state assumption would
110 be indeed valid as long as coke formation rate does not change appreciably over a sufficiently

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111 small time step. Nighswander et al. [7] showed that the quench time (actual gas residence time)
112 required to completely arrest propane pyrolysis reactions in a TLX tube is less than 20 ms. Eqs.
113 (1)–(4) reduce to a system of (j þ 3) simultaneous coupled initial value ordinary differential
114 equations. A detailed discussion of the terms and method of solution for these equations is

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115 provided in following sections.

116 2.1. Kinetic model

117 Coke formation in the thermal cracking of hydrocarbons is a complex phenomenon due to the
118 various possible coke forming free radical reactions and the exact mechanism is still not very clear.
119
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Due to these uncertainties, only simple models involving either the reactant and/or products were
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Table 4
Various coke formation kinetic model
Model I
k1
Naphtha ! products
k2
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Naphtha ! coke
Model II
k1
Naphtha ! products
k3
Aromatics ! coke
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Model III
k1
Naphtha ! products
k4
C6+ ! coke
Model IV
k1
Naphtha ! products
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k5
1,3-C4H6 ! coke
Model V
k1
Naphtha ! products
k6
C2H4 ! coke
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Model VI
k1
Naphtha ! products
k7
C3H6 ! coke
Model VII
k1
Naphtha ! products
k8
Aromatics ! coke
k9
C6+ ! coke
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120 postulated. The carbon–stream reaction was not included in the models, because under these
121 conditions it is not expected to affect the coke deposition. The proposed models were shown that
122 coke can be formed either from the reactant, aromatics C6+, 1,3-butadiene, ethylene, and
123 propylene or from both C6+ and aromatics. The various models investigated are shown in Table
124 4. For each model, the asymptotic rate of coking was expressed in the power law form. The
125 parameters for the various models were determined by Kumar and Kunzru [5] using non-linear

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126 optimization. The sum of squares of the deviations between the calculated and experimental
127 asymptotic coking rates was used as the objective function and minimized by the appropriate

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128 choice of frequency factor, activation energy and reaction order. Model II was preferred over the
129 others because of the significantly lower residual SSQ. Thus, for model II, the expression for the
130 rate of coking can be written as

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

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132 in which k3 ¼ 7:284  1013 and E3 ¼ 273:08  106 .
133 Neither of these models incorporates tube surface catalytic reactions, but it has been shown by
134 Fairburn [1] that these effects are negligible. The radical reaction scheme is expected to be more
135 accurate in describing the reaction kinetics, but it is also more complicated and time consuming
136
137
138
D
from a computational point of view. For propane pyrolysis quenching it was shown by Nighs-
wander et al. [7] that a molecular reaction scheme qualitatively predicts the same kinetic behav-
iour as a far more complex radical reaction scheme with more than 80 reactions that requires
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139 significantly more computational effort. As summarized by Kumar and Kunzru [5], this reaction
140 scheme consists of 22 reactions involving 14 molecular species and an inert steam.

141 2.2. Heat transfer correlation

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142 The overall heat transfer coefficient, U , in Eq. (2) is detailed based on the outside tube area as
143 follows:
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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
145 The terms in Eq. (6) represent the inside fouling factor, the inside convective heat transfer re-
146 sistance, the resistance of the coke layer, the tube wall outside convective heat transfer resistance,
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147 the wall conductive resistance, and the outside fouling factor, respectively. The numerical values
148 for the fouling factors are listed in Table 2. Radiation heat transfer, which was shown to have a
149 negligible contribution to the total heat flux, has been neglected in the equation. The coke thermal
150 conductivity, kc , is dependent on the type of coke formed and can be viewed as an adjustable
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151 parameter. For the parametric studies to be presented later, a value of 2.2 W/m K for kc was used
152 for the base case calculations. The tube wall thermal conductivity, kw , is given by the following
153 expression [8]:
kw ¼ 24:4 þ 0:0041ðT  977:6Þ ð7Þ
155 The inside convective heat transfer coefficient was calculated using the Dittus–Bolter equation as
156 follows:
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H. Manafzadeh et al. / Applied Thermal Engineering xxx (2003) xxx–xxx 7

ðNuÞz ¼ 0:023ðReÞ0:8 0:33

z ðPrÞz ð8Þ
158 This equation does not take into account the heat transfer enhancement in the thermal entrance
159 region. It was shown by Nighswander et al. [7] that the entrance effects on the TLX are not large
160 and Eq. (8) provides a slightly conservative estimate of the heat transfer coefficient. The outside
161 heat transfer coefficient ho is large with respect to hi and as a result the last term in Eq. (6) can be

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162 safely neglected. The calculation of the local Reynolds and Prandtl numbers requires the deter-
163 mination of the average gas transport properties. These were determined from pure component

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164 data with the application of mixing rules.
165 The Fanning friction factor in Eq. (3) was calculated from the following expression for smooth
166 pipes:
0:2
f ¼ 0:046NRe ð9Þ

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168 Finally, the evaluation of heat of reaction (DHRi ) in Eq. (2), the standard heat of formation data
169 for the pure components were obtained from the literature [10].

170 2.3. Coke deposition

171
172
D
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,
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173 operating conditions, pyrolysis equipment, its material of construction and pre-treatment given to
174 the inner walls. The coke deposition model used in this work was derived from the basic coke
175 thickness equation of [6]. His equation represents the rate of coke thickness at a given axial
176 position:
 
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ddc aMc rc
¼ ðDi  2dc Þ ð10Þ
dt 4qc
178 where a is the coke lay-down factor defined as the fraction of coke formed that deposits on the
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179 tube wall, and rc is the rate of coke formation as predicted by the reaction kinetics. It should be
180 noted that the axial dependence of dc arises from the dependence of rc on temperature and thus z.
181 Integration of Eq. (10) yields
aMc rc
Ddc ¼ Dt ð11Þ
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qc
183 Eq. (10) calculates the coke thickness change, dc over a time step Dt. This equation is solved at
184 each time step for the change in coke thickness at each axial position. This change was added to
185 update the total coke thickness for subsequent time steps.
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186 2.4. Physical condensation

187 Due to the temperature variation in TLX between 860 and 360
C, two coke deposition
188 mechanisms have the main role in the exchanger fouling. The first model which is basically
189 chemical is dominated in the first half of the tube while the second model which is based on the
190 physical condensation is dominated in the remaining tube length. Kopinke et al. [4] investigated
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30
25
20
15
10
5
0

ht H6
4

F
2

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

OO
yc
N
en

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

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Table 1
Rates and dew points for the poly-cyclics
Name Rate (mol/h) Dew point (
C)
M-Anthracene 4.34 488
Acenaphthylene 9.54 317
Anthracene
Chrycene
5.64
7.56
D 381
380
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191 the second mechanism and concluded that the relative rate of coke deposition by physical con-
192 densation is related to the rate of formation for poly-cyclic hydrocarbons in the cracking gas. As
193 shown in Fig. 1 the main components of coke deposited in the TLX are acenaphene, anthracene
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194 and chrysene. Therefore, due to the componentÕs dew point, listed in Table 1, the coke will be
195 deposited by condensation of heavy aromatics inside the tube. This phenomenon has been used to
196 predict the thickness of coke deposited in the second half of the exchanger tubes.
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197 3. Model solution

198 For the kinetic scheme, the model described by Eqs. (1)–(3) is actually an initial value problem
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199 involving 32 simultaneous coupled ordinary differential equations. In addition, coke formation as
200 a function of operating time was incorporated through Eq. (4) by repeating the solution of Eqs.
201 (1)–(3) at every time interval. The solution to these equations was obtained by writing a computer
202 program using ‘‘C’’ language. The software may also be run in a personal computer. Additional
203 details of the calculation procedure are described in Manafzadeh (1998).
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204 4. Results and conclusions

205 The operating data for the industrial TLX were supplied by Arak Petrochemical Company
206 (APC), Arak, Iran. A summary of the TLX configuration and average feed compositions and
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Table 2
Operational data of an industrial TLX
Tube length 8.7 m
Tube ID 0.040 m
Tube thickness 0.008 m
Tubes number 130
70 m2

F
Total exchanger area
Steam temperature 325
C
Steam pressure 12 000 kPa

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Cracked gas inlet temperature 866
C
Cracked gas inlet pressure 160 kPa
Cracked gas inlet velocity 100–120 m/s
Tube inside fouling factor, ff i 0.000688 m2 K/W
Tube outside fouling factor, ff o 0.000174 m2 K/W

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

207 conditions provided by APC is described in Tables 2 and 3. Average values of the feed conditions
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208 were used since their actual day-to-day variation is quit small. The olefin plant is consisted of eight
209 naphtha cracking furnaces (seven in operation and one in decoking) each connected to one TLX.
210 Based on the input data listed in Tables 2 and 3, the simulation results of the present work are
211 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
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212
213 i.e. start of run, SOR, middle of run, MOR, and end of run, EOR when the maximum allowable
214 exit temperature is reached and the exchanger is bypassed for decoking operation. This temper-
215 ature is about 440
C in the normal operation. The results are obtained for a coke deposition
216 factor of 0.225. As shown in Fig. 2, the coke deposition results in a decreased rate of heat transfer
217 causing the quench time steadily increase with operating time. The quench time is defined as the
218 actual time which the reaction kinetics predicts no appreciable further reaction. The predicted
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10 H. Manafzadeh et al. / Applied Thermal Engineering xxx (2003) xxx–xxx

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

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

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219 coke thickness on the tubes of the exchanger for the MOR and EOR operation times are shown in
220 Fig. 3.
221 The coke deposited mainly in the second half of the tubes and concentrated at the tube outlet.
222 There are two main parameter to control the heat transfer in the TLX; the exit cracked gas
223 temperature and the outlet pressure inside the tubes.
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224 Fig. 4 illustrates the predicted pressure profile inside the exchanger tubes at various operating
225 times, SOR, MOR and EOR. With the increased coke deposition, the tube pressure drop increases
226 sharply. The majority of this increase occurs at the tube entrance where the largest deposition of
227 coke is predicted. The results show that the maximum pressure drop inside the tubes will be 60
228 kPa at the end of operation time when the exchanger must be decoked. Having established a
229 match of the industrial data at Day 0 (start of run) the coke formation model was introduced to
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H. Manafzadeh et al. / Applied Thermal Engineering xxx (2003) xxx–xxx 11

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

D
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EC

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

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

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12 H. Manafzadeh et al. / Applied Thermal Engineering xxx (2003) xxx–xxx

230 predict the TLX outlet temperature after 63 days of operation. This was done by adjusting the
231 coke lay-down factor, a until an acceptable match of he Day 63 data provided by APC was
232 obtained. The predicted effect of a at Day 63 on the TLX outlet temperature is shown in Fig. 5. It
233 is observed from the figure that the predicted TLX outlet temperature is within 1
C of the in-
234 dustrial data for values of a between 0.20 and 0.23. Fig. 6 shows the effect of coke lay-down factor
235 on the pressure distribution inside the tubes. It is shown from the figure that the predicted outlet

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236 pressure remains in the range provided by APC for values of a less than 0.3. In other words, it can
237 be concluded that a must be between 0.2 and 0.3 to much the industrial data. Therefore for this

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238 particular exchanger an a of approximately 0.225 provides a good approximation of the TLX
239 operational time history.

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240 5. Conclusions

241 A comprehensive model of a TLX tube in industrial gas quenchers has been developed. The
242 model incorporates a semi-empirical coke formation equation to predict a coke deposition rate
243 both chemically and physically and the effect of this coke on the TLX steady state and operational
244 time performance. The agreement between the results shows the accuracy of the mathematical
245
246 APC to control the TLX.
D
model. The model and simulation software presented here is used as a guide for plant operators in
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247 Acknowledgements
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248 The authors would like to thank Arak Petrochemical Company for providing the industrial
249 TLX data. The financial support from the National Petrochemical Company (NPC) is gratefully
250 acknowledged.
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251 References

252 [1] J.A. Fairburn, Ultrapyrolysis of n-hexadecane in a Novel Micro-Reactor, M.Sc. Thesis, University of Calgary,
253 Alta., Canada, 1988.
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254 [2] R.S. Huntrods, M. Eng. Thesis, University of Calgary, Calgary, Canada, 1988.
255 [3] R.S. Huntrods et al., Modeling of coke formation in gas quenchers of industrial ethane cracking furnace, Chem.
256 Eng. Res. Des. 67 (1989) 632–638.
257 [4] F.D. Kopinke, G. Bach, G. Zimmermann, New results about TLE fouling, J. Anal. Appl. Pyro. 27 (1993) 45–55.
258 [5] P. Kumar, D. Kunzru, Kinetics of coke deposition in naphtha pyrolysis, Can. J. Chem. Eng. 63 (1985) 598.
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259 [6] I. Lichtenstein, Chem. Eng. Prog. 60 (12) (1964) 64.

260 [7] J.A. Nighswander, S.H. Richard, A.K. Mehrotra, L.A. Behie, Quench time modeling in Propane Ultra pyrolysis,
261 Can. J. Chem. Eng. 67 (1989) 608.
262 [8] H.F. Rase, Chemical Reactor Design for Process Plants, in: Case Studies and Design Data, vol. 2, John Wiley, New
263 York, 1977.
264 [9] K.M. Sundaram, G.F. Froment, Chem. Eng. Sci. 35 (1977) 601.
265 [10] J. Towfighi, A. Niaee, R. Karimzadeh, A kinetic model for the simulation of thermal cracking reactors in the olefin
266 plant, Iranian J. Sci. Tech. 55 (2) (1995) 68–75.