Académique Documents
Professionnel Documents
Culture Documents
discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/265338956
READS
375
5 AUTHORS, INCLUDING:
Marziyeh Hamidi
M. R. Rahimpour
Shiraz University
8 PUBLICATIONS 25 CITATIONS
SEE PROFILE
SEE PROFILE
ARTICLE IN PRESS
chemical engineering research and design x x x ( 2 0 1 4 ) xxxxxx
Department of Chemical Engineering, Amirkabir University of Technology, No. 424, Hafez Ave., Tehran, Iran
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University,
Shiraz 71345, Iran
c Petroleum Engineering Department, Islamic Azad University, Science and Research Branch, Fars, Iran
b
a b s t r a c t
In this study, liquid furnace has been investigated to nd out the reason of over-cracking which results in excessive tar
and coke formation so that the furnace run length is decreased. For this purpose, a one-dimensional mathematical
model is used to analyze the furnace temperature prole. In addition, inlet feedstocks and outlet gas products of
furnace have been studied. The results obtained from the simulation demonstrate differences between modeled coil
outlet temperature and cracking severity with those of experimental data. For overcoming this problem, furnace
temperature were sufciently reduced with the purpose of reaching constant cracking severity at 0.5. Correction of
the coil outlet temperature led to signicant increase in cracking severity, propylene production, furnace capacity
and run length while gasoline production and number of decoke cycles decreased.
2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Naphtha; Thermal cracking; Mathematical modeling; Over-cracking; Furnace run length
1.
Introduction
Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
http://dx.doi.org/10.1016/j.cherd.2014.08.010
0263-8762/ 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
chemical engineering research and design x x x ( 2 0 1 4 ) xxxxxx
Mass fraction
Light end
Rafnate
LPG
C5 cut
C5 +
Propane recycle
C4 cut recycle
21,645
11,995
2620
1736
2873
937
8390
0.4312
0.2390
0.0522
0.0346
0.0572
0.0187
0.1671
2.
Process description
2.1.
Convection section
Since the radiant coil operates at high temperature, the residual part of the red duty is recovered in the furnace convection
section. At each furnace, the feed and dilution steam are
heated by ue gas in their respective convection banks prior
to mixing. The purpose of these convection banks is to heat
the feed/steam mixture to the required radiant coil inlet temperature.
2.2.
Radiant section
2.3.
In order to stop the reaction at the radiant coil outlet, the pyrolysis product is rapidly cooled, or quenched, in the transfer line
exchanger (TLE) by several hundred degrees in a time interval
of milliseconds.
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
Feedstock
Mass fraction
Parameter
Value
Light end
Rafnate
LPG
C5 cut
C5 +
Propane recycle
C4 cut recycle
0.70
0
0
0.03
0.03
0.1
0.14
GK5
2
1
12.068
13.028
0.048
0.068
0.006
0.0065
950
1110
600
865
2.6
2.05
2.0
781.25
390.625
0.5
3.
Complications associated with the
furnace
The liquid furnace problems are:
(1) The liquid furnace feed is not the same as design ow
rate, therefore, furnaces operating conditions should be
regulated according to the received feed so that the outlet
products be in the optimal condition.
(2) When the furnace is adjusted at its full capacity, the fuel
gas pressure guard restricts the fuel gas ow to prevent
the emergency furnace shutdown. Once the pressure of
gas fuel in furnace exceeds its allowable limit (2.2 bar),
emergency shutdown alarm system of furnace will be
activated and furnace efuent temperature will decline
below 865 C. For overcoming this problem, according to
the feed specications, the furnace should operates at its
90% capacity to control coil outlet temperature at 854 C.
(3) All furnaces have been designed to achieve a run length
of at least 60 days, but average of their run length never
exceeds 45 days. This problem leads to reduction in
operating time and repetition of furnace decoking which
increases usage of utilities and expenditure more time
compared with ordinary operation.
To overcome these problems, inlet feed and outlet gas
product of furnace have been investigated. During this study,
received feed composition was nearly constant. The composition of feed and its analysis are presented in Tables 2 and 3,
respectively.
The properties of liquid furnace coil are provided in Table 4.
The sample of liquid furnace outlet gas was analyzed
with Renery Gas Analyzer (RGA) with detection accuracy of
0.01 mol%. The analysis of gaseous samples has been done
Mass fraction
Propane
Vinyl acetylene
n-Butane
i-Butane
22-Mbutane
tr2-Butene
1-Butene
i-Butene
2M-1-butene
n-Pentane
i-Pentane
2-Mpentane
3-Mpentane
Cyclopentene
n-Hexane
0.11
0.005
0.285
0.02
0.01
0.006
0.05
0.014
0.01
0.21
0.205
0.025
0.015
0.02
0.015
4.
Kinetic model
The kinetic model could be sorted into three kinds: molecular reaction kinetic model, empirical model and mechanism
model of free radical reaction (Geng et al., 2012).
Among different models for naphtha cracking, a set of 22
molecular reactions have been proposed in current work. 20
reactions of them are postulated by Gao et al. (2009) in addition
to 8 radical reactions and 7 coke formation reactions are based
on Zou et al. (1993) model.
(1)
2C2 H6 C3 H8 + CH4
(2)
C3 H8 C2 H4 + CH4
(3)
C4 H10 C3 H6 + CH4
(4)
C4 H10 2C2 H4 + H2
(5)
C4 H10 C2 H4 + C2 H6
(6)
C4 H8 C4 H6 + H2
(7)
vC3 H5 C2 H2 + CH3
(8)
Reversible reactions
C2 H6 C2 H4 + H2
C3 H6 C2 H2 + CH4
(9)
(10)
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
chemical engineering research and design x x x ( 2 0 1 4 ) xxxxxx
C4 H10 C4 H8 + H2
(11)
C3 H8 C3 H6 + H2
(12)
r1 = k1
C3 H4
C3 H4
(13)
r2 = k2
1-C4 H8 2-C4 H8
H
(14)
(15)
H + 2-C4 H8 2-C4 H9
(16)
H + 1-C4 H8 i-C4 H9
(17)
+ 1-C4 H8 1-C4 H9
r3 = k3
r4 = k4
r5 = k5
1-C4 H9 C2 H4 + C2 H5
(18)
C2 H5 + C2 H5 n-C4 H10
(19)
H + C3 H4 vC3 H5
(20)
H + C3 H4
aC3 H5
r6 = k6
r7 = k7
(21)
r8 = k8
F
(22)
C3 H8 + C2 H4 C2 H6 + C3 H6
(23)
2C3 H6 3C2 H4
(24)
(25)
C2 H2 + C2 H4 C4 H6
(26)
C2 H4 + C2 H6 C3 H6 + CH4
(27)
(28)
C3 H6 + C4 H6 C7 H8 + 2H2
(29)
C4 H8 + C4 H6 C8 H10 + 2H2
C4 H6 + C4 H6 C8 H8 + 2H2
C2 H4 Coke
C6 H6 Coke
(34)
C7 H8 Coke
(36)
C4 H6 Coke
(37)
Ft
(42)
RT
F
P
C4 H10
Ft
(43)
RT
F
P
C4 H10
Ft
RT
C4 H8
P
F
(44)
Ft
(45)
RT
F
P
vC3 H5
Ft
(46)
RT
Reversible reactions
r9 = k9
F
r11 = k11
RT
F
C4 H10
C4 H10
Ft
P
FC3 H4
Ft
RT
1-C4 H8
P
F
Ft
RT
F1-C4 H8 FH
RT
F2-C4 H8 FH
P 2
t
Ft2
RT
F1-C4 H8 FH
P 2
t
Ft2
F
1C4 H9
Ft
RT
P
t
RT
FC2 H5 FC2 H5
FH FC3 H4
Ft
P 2
RT
P
RT
2-C4 H8
P
1-C4 H9
P
t
Ft
RT
F
2-C4 H9
P
t
Ft
RT
Fi-C4 H9
P
t
RT
Ft
FC2 H4 FC2 H5
kR20
P 2
t
Ft2
kR19
(52)
RT
F
(51)
Ft
kR17
(50)
Ft
RT
FC3 H4
F
kR18
RT
kR16
(49)
P 2
Ft 2
kR15
P 2
Ft2
kR14
Ft2
kR13
P 2
RT
FC3 H6 FH2
(48)
P 2
Ft 2
kR12
RT
RT
FC4 H8 FH2
P
P 2
Ft 2
(47)
RT
FC2 H2 FCH4
kR11
RT
F
r17 = k17
kR10
Ft 2
P
Ft
r16 = k16
r20 = k20
Ft
r18 = k18
P
C 3 H6
P 2
FC2 H4 FH2
kR9
RT
F
r13 = k13
r14 = k14
Ft
P
C2 H6
(38)
P
C4 H10
r19 = k19
C8 H10 Coke
(41)
RT
F
(35)
C8 H8 Coke
Ft
(32)
(33)
P
C3 H8
r15 = k15
C3 H6 Coke
(40)
RT
F
Coke formation reactions
Ft
(30)
(31)
P
C2 H6
r12 = k12
C2 H4 + C4 H6 C6 H6 + 2H2
(39)
RT
F
r10 = k10
C3 H6 + C2 H6 C4 H8 + CH4
Ft
P
C6.5 H14
RT
F
n-C4 H10
P
t
Ft
RT
vC3 H5
P
F
Ft
RT
(53)
(54)
(55)
(56)
(57)
(58)
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
r21 = k21
P 2
FH FC3 H4
Ft2
RT
kR21
F
aC3 H5
Ft
P
t
RT
(59)
Rate coefcient
r22 = k22
Ft2
r23 = k23
r24 = k24
FC3 H8 FC2 H4
FC3 H6 FC3 H6
FC2 H6 FC3 H6
r27 = k27
FC2 H2 FC2 H4
FC2 H6 FC2 H6
FC2 H4 FC4 H6
FC3 H6 FC4 H6
P 2
t
P 2
t
P 2
t
P 2
t
RT
FC4 H8 FC4 H6
Ft2
P 2
RT
Ft2
r30 = k30
RT
Ft2
r29 = k29
P 2
RT
Ft2
r28 = k28
RT
Ft2
P 2
RT
Ft2
r26 = k26
RT
Ft2
r25 = k25
P 2
RT
Ft2
r31 = k31
FaC3 H5 FC3 H6
P 2
t
RT
FC4 H6 FC4 H6
Ft2
P 2
t
RT
k1
k2
k3
k4
k5
k6
k7
k8
k9
kR9
k10
kR10
k11
kR11
k12
kR12
k13
kR13
k14
kR14
k15
kR15
k16
kR16
k17
kR17
k18
kR18
k19
kR19
k20
kR20
k21
kR21
k22
k23
k25
k26
k27
k28
k29
k30
k31
k32
k33
k34
k35
k36
k37
k38
(60)
(61)
(62)
(63)
(64)
(65)
(66)
(67)
(68)
(69)
r33 = k33
r34 = k34
r35 = k35
r36 = k36
r37 = k37
r38 = k38
F
C2 H4 Pt
1.34
(70)
Ft RT
F
C3 H6 Pt
1.34
(71)
Ft RT
F
C6 H6 Pt
1.34
(72)
Ft RT
F
C7 H8 Pt
1.37
C8 H8 Pt
C4 H6 Pt
(74)
1.37
(75)
Ft RT
F
C8 H10 Pt
Ft RT
5.
1.37
Ft RT
F
6.565E+11
3.750E+12
4.692E+10
7.000E+12
7.000E+14
4.099E+12
1.000E+10
1.585E+12
7.943E+13
7.943E+08
5.012E+13
7.943E+08
1.637E+12
1.780E+04
5.888E+10
9.030E+02
3.162E+13
1.585E+13
2.239E+12
1.950E+12
2.512E+10
1.288E+13
1.000E+11
1.000E+14
1.000E+11
1.000E+14
1.514E+14
1.995E+08
1.995E+09
5.012E+16
3.467E+10
1.412E+12
3.467E+10
8.912E+12
6.026E+07
2.536E+10
1.000E+11
1.026E+09a
7.083E+10a
8.385E+06
9.740E+05
5.610E+11
1.510E+06
5.000E+14
2.770E+09
5.610E+18
1.390E+12
1.390E+12
1.390E+12
1.390E+12
E (J/mol)
2.20E+05
2.73E+05
2.12E+05
2.49E+05
2.95E+05
2.56E+05
2.09E+05
1.57E+05
2.97E+05
1.59E+05
2.93E+05
1.59E+05
2.61E+05
1.35E+05
2.15E+05
9.34E+04
2.64E+05
2.57E+05
2.51E+05
2.59E+05
8.37E+03
1.63E+05
1.05E+04
1.72E+05
8.37E+03
1.59E+05
1.30E+05
3.18E+04
0
3.47E+05
8.37E+03
1.57E+05
8.37E+03
2.47E+05
9.00E+04
2.47E+05
2.51E+05
1.73E+05
2.53E+05
1.44E+05
1.49E+05
2.42E+05
1.24E+05
2.24E+05
1.16E+05
2.74E+05
1.41E+05
1.41E+05
1.41E+05
1.14E+05
(73)
Ft RT
F
A (s1 )
1.37
(76)
Mathematical modeling
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
875
850
dj
dz
Mj
G
rri S(i.j)
(77)
4
dT =
G Cp
rri Hi + Uo (Te T)
dZ
D
Temperature (C)
825
775
COT at measuring point
750
725
700
675
(78)
650
625
600
(79)
d
G2
2F G2
dp
= 2
dz
gD
g dz
(80)
Re0.2
D
(81)
f = 0.092
Re0.2
+
D
D
(82)
0.7 + 0.35
90
0.051 + 0.19
D
Rb
(83)
The rate of coke formation can be calculated from the following equation:
Mc rc
C
= (D 2tc )
t
4c
6.
(84)
Model solution
7.
Simulated COT
800
Model validation was carried out by comparing the mathematical modeling results with the design data in the
manufactures documents over 195 operating days. Table 6
compares modeling results and design data. As can be seen,
they were in good agreement, while comparison between
experimental data and model results indicated that they were
not the same. For eliminating this error, sampling was done
with more accuracy, but new data conrmed the differences
between experimental and modeling results again.
For matching the modeling results to cracked gas analysis,
furnace temperature was sufciently reduced with the purpose of reaching constant cracking severity at 0.5. Furnace
efuent temperature declined from 865 C to 850 C as a consequence of reduction in furnace temperature.
10
12
14
16
18
20
22
24
26
28
30
7.1.
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
Hydrogen
Methane
Acetylene
Ethylene
Ethane
Methyl-acetylene
Propadiene
Propylene
Propane
Vinyl-acetylene
Butadiene
Butane (sum)
Butane (sum)
Total C5 -C9 s
Total C10 +
Carbon oxide
Carbon dioxide
1.0856
19.526
0.78517
32.721
3.4519
0.7691
0.49128
16.676
0.85702
0.095277
4.4897
5.0575
2.3919
10.106
1.3736
0.11502
0.008071
Relative error %
1.4579
4.4171
12.1641
1.4428
0.3459
9.8714
22.82
1.3254
28.5817
5.8633
1.9716
3.6373
5.0833
2.8269
8.1575
4.5636
19.29
1.07
18.7
0.7
33.2
3.44
0.7
0.4
16.9
1.2
0.09
4.58
4.88
2.52
10.4
1.27
0.11
0.01
26
C5+
Methane
Modeled Methane @865C
Modeled C5+ @865C
24
30
Ethylene
Propylene
Modeled Ethylene@865C
Modeled Propylene@865C
20
18
COT=865C
2013/1/17
COT=850C
16
Yield (Wt %)
Yield (Wt %)
22
25
COT=865C
2013/1/17
COT=850C
20
14
15
12
10
(2012/10/9)20 37 42 55 58 64 70 77 82 100102111133140145146170175 (2013/4/21)
Time (day)
10
Tima (day)
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
1050
0.54
0.52
Severity
0.5
2013/1/17
0.48
COT=865C
COT=850C
0.46
0.44
0.42
0.4
(2012/10/9) 20 37 42 55 58 64 70 77 82 100102111133140145146170175 (2013/4/21)
COT= 865c
COT= 855c
COT= 845c
1000
950
900
850
800
750
Time (day)
10
12
14
20
22
24
26
1080
Average tube skin temperature
Maximum tube skin temperature
620
600
Product (ton/day)
18
640
580
560
540
2013/1/17
COT=865C
COT=850C
520
1070
1060
1050
1040
2013/1/17
1030
COT=850C
COT=865C
1020
500
480
16
Propylene Product
Gasoline Product
1010
(2013/1/13) 3
10 11 12 13 14 15 16 17
(2013/1/31)
(2013/1/9) 3
9 10 11 12 13 14 15 16 17 18 19 (2013/1/29)
Time (day)
Time (day)
3
COT=865 c
COT=855 c
COT=845 c
50
Run Length(day)
Coking rate(mm/month)
2.5
60
1.5
40
30
20
10
0.5
0
0
10
12
14
16
18
20
22
24
Coil length(m)
26
2
3
Number of Operating Cycle
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
ARTICLE IN PRESS
4
x 10
5.2
5800
5600
5400
4.8
5200
5000
4.6
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
4.4
35
Time (day)
8.
Conclusion
Nomenclature
C
C1 , C2
C p
D
Fi
f
G
g
Hi
ki
Mj
Mc
Pt
p
R
Rb
Re
rn
rc
rri
S(i,j)
T
Te
Tg
T
t
tc
U
U0
z
Greek letters
heat of reaction (kJ/mol)
H
parameter of tube bend
process gas specic gravity (kg/m3 )
c
coke specic gravity (kg/m3 )
coking factor
angle of bend
References
Basu, B., Kunzru, D., 1992. Catalytic pyrolysis of naphtha. Ind.
Eng. Chem. Res. 31, 146155.
Bajus, M., Vessely, V., Leclercq, P.A., Rijks, J.A., 1980. Steam
cracking of hydrocarbons. 3. Straight-run naphtha. Ind. Eng.
Chem. Prod. Res. Dev. 19, 556563.
Choudhary, V.R., Mulla, S.A.R., 2001. Energy efcient
simultaneous oxidative conversion and thermal cracking of
ethane to ethylene using supported BaO/La2 O3 catalyst in the
presence of limited O2 . Appl. Energy 68, 377386.
Edwin, E.H., Balchen, J.G., 2001. Dynamic optimization and
production planning of thermal cracking operation. Chem.
Eng. Sci. 56, 989997.
Gao, G.Y., Wang, M., Pantelides, C.C., Li, X.G., Yeung, H., 2009.
Mathematical modeling and optimal operation of industrial
tubular reactor for naphtha cracking. Comput. Aid. Chem.
Eng. 27, 501506.
Geng, Z., Cui, Y., Xia, L., Zhu, Q., Gu, X., 2012. Compromising
adjustment solution of primary reaction coefcients in
ethylene cracking furnace modeling. Chem. Eng. Sci. 80,
1629.
Ghashghaee, M., Karimzadeh, R., 2011. Multivariable
optimization of thermal cracking severity. Chem. Eng. Res.
Des. 89, 10671077.
Heynderickx, G.J., Schools, E.M., Marin, G.B., 2006. Simulation of
the decoking of an ethane cracker with a steam/air mixture.
Chem. Eng. Sci. 61, 17791789.
Jianxin, Zh., Hong, X., Xiaojian, L., Xiang, L., 2012. Inuence of the
SiO2 /S coating and sulfur/phosphorus-containing coking
inhibitor on coke formation during thermal cracking of light
naphtha. Fuel Process. Technol. 104, 198203.
Maciel Filho, R., Sugaya, M.F., 2001. A computer aided tool for
heavy oil thermal cracking process simulation. Comput.
Chem. Eng. 25, 683692.
Mei, C.S., Wen, P.Y., Liu, Z.C., Liu, H.X., Wang, Y.D., Yang, W.M.,
Xie, Z.K., Hua, W.M., Gao, Z., 2008. Selective production of
propylene from methanol: mesoporosity development in high
silica HZSM-5. J. Catal. 258, 243249.
Pinter, A., Tungler, A., Nagy, L., Vida, L., Kovacs, I., Kerezsi, J., 2004.
A laboratory steam-cracking reactor to characterize raw
materials. Int. J. Chem. Reactor Eng. 2, 15426580.
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010
10
ARTICLE IN PRESS
chemical engineering research and design x x x ( 2 0 1 4 ) xxxxxx
Wang, G., Xu, Ch., Gao, J., 2008. Study of cracking FCC naphtha in
a secondary riser of the FCC unit for maximum propylene
production. Fuel Process. Technol. 89, 864873.
Xu, T., Zhang, Q., Song, H., Wang, Y., 2012. Fluoride-treated
H-ZSM-5 as a highly selective and stable catalyst for the
production of propylene from methyl halides. J. Catal. 295,
232241.
Xu, X., Li, Ch., Shan, H., 2011. Effect of phosphorus on novel
bifunctional additives for enhancing the production of
propylene and removal of SO2 in FCC process. J. Mol. Catal. A:
Chem. 340, 99107.
Zou, R., Lou, Q., Mo, S., Feng, S., 1993. Study on a kinetic model of
atmospheric gas oil pyrolysis and coke deposition. J. Ind. Eng.
Chem. 32, 843847.
Please cite this article in press as: Barazandeh, K., et al., Investigation of coil outlet temperature effect on the performance of naphtha cracking
furnace. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.08.010