Olefin Thermal Cracking
Olefin Thermal Cracking
Olefin Thermal Cracking
4, 2010
Olefin Production
from Heavy Liquid Hydrocarbon Thermal Cracking:
Kinetics and Product Distribution
INTRODUCTION
Steam cracking of various hydrocarbons is the major tendency to the heavier hydrocarbon such as gasoil and
rout for production of light olefins, ethylene and propylene, residue as feedstocks for olefin production.
which are basic feedstocks for the petrochemical industries. Thermal cracking of atmospheric gasoil was carried
Steam is used in this process to increase the olefin out by Hirato et al. [2]. Then, molecular-based model
selectivity and decrease coke formation rate. The mixed was developed. They also used the modified model for
hydrocarbon and steam are heated to primary cracking modeling of thermal cracking of naphtha and kerosene.
temperature (500 - 650°C). Then, it is cracked in fired Belohlav et al. [3] developed a model of pyrolysis of
tubular reactor where the reactions take place at higher ethane, petroleum gases, and primary naphthas involve
temperatures. free radical reactions. The kinetic model optimization and
Free-radical chain reactions are accepted as reaction verification was performed by the experimental set.
mechanism of hydrocarbon thermal cracking [1]. The increase Thermal cracking of kerosene for producing ethylene and
in prices of lighter hydrocarbons has brought about the propylene has been studied in an experimental setup
* To whom correspondence should be addressed.
+ E-mail: towfighi@modares.ac.ir
1021-9986/10/4/135 13/$/3.30
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by Ghassabzadeh et al. [4]. An applicable kinetic model Table 1: Chemical composition and physicochemical characteristics
was developed to predict yield distribution of products of of heavy liquid hydrocarbon feed.
the kerosene thermal cracking. Therefore, a reaction Chemical composition (wt%)
mechanism is generated on the basis of major reactions
n - Paraffin 26.65
classes in the pyrolysis and feed compounds using some
I - paraffin 28.29
simplification assumptions in the model. Zahedi et al. [5]
studied the thermal cracking of atmospheric gas oil. Naphthene 17.84
The obtained maximum yield of ethylene was equal to Aromatics 19.3
30.9 wt% as well as the maximum yield of propylene
Olefins 0.17
was 12.2wt%. A mechanistic model was developed based
on experimental data. Depeyre et al. [6] studied the Physiochemical properties
effects of temperature, steam to gas oil ratio and Hydrocarbon C15+ 7.75 wt%
residence time on major products in gas oil thermal Specific Gravity 0.769 g/g
cracking. The best yield of ethylene, 27% in mass,
Average Molecular Weight g 148.35
was obtained in the quartz reactor at 770 °C, residence
time of 0.6 s, and mass ratio of steam to gas oil equal to Sulfur wt ppm 2137
1. Keyvanloo et al. [7] studied the effect of main Mercury 1.13 wt ppb
parameters and their quadratic and cubic interactions on
Lead ppb wt 3.9
the yield of light olefins in thermal cracking of naphtha
by statistical design of experiments. They have found Arsenic 6.5 wt ppb
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Exchanger
Exchanger
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Experimental Data
CH4 8.72 16.3 15.00 8.34 13.25 15.77 14.93 9.35 13.27
C2H6 3.72 1.82 1.93 2.5 2.27 2.2 2.00 3.41 2.23
C2H4 19.75 29.9 28.34 18.53 25.8 30.09 27.8 20.74 25.3
C3H8 1.75 0.67 0.93 1.49 1.22 0.84 0.94 1.18 1.25
C3H6 13.21 9.45 12.05 14.03 14.31 10.4 11.85 13.31 14.41
C4H8 3.71 1.47 1.95 3.51 2.26 1.74 2.07 3.44 2.26
Run 10 11 12 13 14 15 16 17
Steam ratio (g/g) 1.22 1.22 0.5 0.95 0.95 0.95 1.22 1.4
Experimental Data132.8
Momentum balance: Λ dt
ζ = 0.7 + 0.35 0.051 + 0.19 (6)
90 Rb
1 Pt dPt d 1 1 1 dT
− = + + Fr (4)
Mm Pt 2
ηG RT dz dz M m Mm T dz Where Rb and Λ represents the radius of the tube
bend and angle of bend, respectively. Towfighi et al. [12]
Which Fr is the friction factor and is calculated have shown the detail description of the applied
as follow: mathematical model.
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Yield (we%)
reaction [13,14]. As shown in Table 1, the feed analysis 30
contains n-paraffins, iso-paraffins, naphthenes and
aromatics. 20
The proposed kinetic model is semi-mechanistic
10
model of radical decomposition based on the simplified
theory of radical and pure molecular reactions.
0
The radical reactions contain chain-initiation reactions, 760 800 840 880 920
chain-propagation reactions, chain-termination reactions,
secondary reaction, and isomerization reaction [15-16]. COT (°C)
Molecular reactions contain dehydrogenation, Diels-Alder
molecular reaction and isomerization reaction. The developed
T = 840 °C, SR = 1.24 g/g
model delete consists of the following reaction: 50
(b)
40
• Radical reaction
1- Chain-initiation reaction, for example:
Yield (we%)
30
C9H20 C5H110 + 1-C4H90
20
2- Chain-propagation reaction, for example:
a) C9H190 C2H4 + C7H150 10
b) C9H20 + H0 C9H190 + H2
0
0.13 0.18 0.23 0.28
3- Chain-termination reaction, for example:
C2H50 + H0 C2H6 Residence time (s)
• Molecular reaction 30
1- Olefin isomerization, for example:
1-C6H110 2-C6H110 20
4- Other molecular reaction, for example: Fig. 2: Effect of (a) COT(°C), (b) residence time(s) and
C3H8 C2H4 + CH4 (c) steam ratio (g/g) on the yield of C2H4, C2H6, C5+.
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Yield (wt %)
45 40
40 35
35
30
Predicted (wt%)
30
Yield (wt%)
25
25
20
20
15
15
10 10
5 C2H4 (exp) C3H6 (exp) C5+ (exp) 5
C2H4 (model) C3H6 (model) C5+ (model)
0 0
750 800 850 900 0 10 20 30 40
COT (°C) Experimental (wt%)
Fig. 3: Effect of COT (oC) on C2H4, C3H6 and C5+ yields Fig. 4: Scatter diagram of C2H4, C3H6 and C5+ yield.
predicted by developed model.
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15
value and then decreases.
10
CONCLUSIONS
5 The goal of this study was to obtain experimental data
on thermal cracking of a heavy liquid hydrocarbon and
0
0 0.2 0.4 0.6 0.8 1 1.2 to develop a kinetic model in order to predict product
distribution of olefins. Central composite design was used
Length (m)
to carry out the experiments. Regarding the results,
Fig. 5: Profile of yields of main products along the reactor at the maximum yield of ethylene and propylene was obtained
residence time=0.3 sec, COT=850 °C, steam ratio=0.6.
30.37 wt% and 15.37 wt%, respectively. Increasing
temperature, residence time and steam ratio increases
it decreases. This is due to the fact that propylene the ethylene yield. But there is a limitation for propylene
was produced at primary reaction and after duration of time, by increasing the operating parameters and its
it was consumed in secondary reactions [7]. Fig. 2(b) shows optimum amount was found at 825°C.
that with the increase of residence time, the ethylene yield Finally, the developed kinetic model was compared
increases, whereas both propylene yield and C5+ yield with experimental data. There was a good agreement
decreases. In order to achieve high ethylene yield, between model results, which is based on free radical
the residence time should be increased. However, chain reactions, and experimental data. Furthermore,
the yield of propylene should be considered. the trends of main products were studied along the reactor.
Fig. 2(c) shows the effect of steam ratio on the yields
of ethylene, propylene and heavy compound. It is shown Acknowledgements
that yield of ethylene increases with increasing the steam Financial support from Chemical Engineering Center
ratio, while C5+ and propylene decrease. In Table 3, of Excellence at Tarbiat Modares University is highly
the maximum yield of ethylene is 30.37 wt% at COT, appreciated.
residence time and steam ratio of 869 oC, 0.208 sec
and 1.22 (g/g), respectively. The maximum yield of
Notation
propylene is 15.37 wt% at COT, residence time and steam ratio
COT Coil outlet temperature, oC
of 825 oC, 0.147 sec and 0.95 (g/g), respectively.
CPj Specific heat capacity of jth component, J/mol K
The model was developed to determine the product
dt Diameter of reactor tube, m
yields in the total mentioned ranges. Fig. 3 shows
Fj Molar flow rate of jth component, mol/s
the effect of temperature on ethylene, propylene
Mm Molecular weight of mixture, g/mol
and C5+ yields in both experiment and model results.
Q Heat flux, kW/m3
Results of the experiment and model for different
rri Rate of reactions, mol/m3·s
conditions are shown in Table 4. As it was shown,
Re Reynolds number
there is a good consistency between experimental and
model data.
Fig. 4 shows a typical scatter diagram for products
distribution of heavy liquid hydrocarbon. It indicates
a good agreement between the predicted and experimental
Received : Dec. 30, 2009 ; Accepted : Apr. 30, 2010
data.
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Table 5 (Continued)
Parameters Adopted
No.
Reaction
LOG (A)1 E2
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Table 5 (Continued)
Parameters Adopted
No. Reaction
LOG (A)1 E2
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Table 5 (Continued)
Parameters Adopted
No. Reaction
LOG (A)1 E2
95 H2 + C3H5 → H + C3H6
0
10.5 20.0
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Table 5 (Continued)
Parameters Adopted
No. Reaction
LOG (A)1 E2
119 C5H10 + H 0
→ C5H9 + H2 12.0 8.0
6. Secondary Reaction II
7. Molecular Reaction I
8. Molecular Reaction II 7
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