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Olefin Thermal Cracking

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Iran. J. Chem. Chem. Eng. Vol. 29, No.

4, 2010

Olefin Production
from Heavy Liquid Hydrocarbon Thermal Cracking:
Kinetics and Product Distribution

Sedighi, Mehdi; Keyvanloo, Kamyar; Towfighi Darian, Jafar*+


Faculty of Chemical Engineering, Tarbiat Modares University,
P.O. Box14115-143 Tehran, I.R. IRAN

ABSTRACT: Thermal cracking of a heavy liquid hydrocarbon was performed in a laboratory


scale tubular reactor. Central Composite Design (CCD), was used as an experimental design
method. The design variables were Coil Outlet Temperature (COT), feed flow and rate steam ratio.
Maximum yield of ethylene was 30.37 wt% at COT, residence time and steam ratio of 869oC, 0.208 s
and 1.22 g/g, respectively. Maximum yield of propylene was 15.37 wt% at COT, residence time and
steam ratio of 825oC, 0.147 s and 0.95 g/g, respectively. A mechanistic model based on free radical
chain reactions was developed using experimental results. Developed reaction network contains
148 reactions for 43 species. Finally, the experimental data were compared with model results.
Scatter diagrams showed good agreement between model and experimental data.

KEY WORDS: Thermal cracking, Heavy liquid hydrocarbon, Kinetic model.

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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Iran. J. Chem. Chem. Eng. Sedighi M. et al. Vol. 29, No. 4, 2010

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

that the higher interactions should be considered


in the modeling of naphtha steam cracking besides Thermal Cracking Set-up
the effect of key factors. A schematic diagram of the experimental set-up
Various multiobjective optimizations have been also is shown in Fig. 1. The hydrocarbon and dilution water
carried out. The other authors [8-10] have also studied the are fed into the preheaters by two dosing pumps and then
thermal cracking and mathematical modeling of different mixture was injected into the reactor at the required flow rate.
feedstock. The setup is controlled by computer [1]. The reactor
In this paper, thermal cracking of a heavy liquid is a tube that is 1.2 m long and has an internal diameter of
hydrocarbon was experimentally investigated and 10 mm and outer diameter of 12.7 mm. The temperature
products yield distribution was studied. Several of each zone was controlled by separate proportional
experiments were conducted to study the effects of controllers. The axial temperature profile was measured
operating parameters on product distribution. In order to using a type K thermocouple. Double-pipe heat
generate systematic experimental data, response surface exchanger was used to cool reactor effluents to
methodology was used. Then a mechanistic model based the appropriate temperature. A fraction of the product gas
on free radical chain reactions was developed to predict is then withdrawn for the analysis via Varian Chrompack
product distribution. CP3800 gas chromatograph, whereas the remainder
is sent directly to the flare.
EXPERIMENTAL SECTION
Feed Characteristics Experimental Design and Collection of Data
The selected feed was a heavy liquid hydrocarbon. CCD method was applied with three design factors,
This feed is the mixture of three industrial residue which namely the hydrocarbon feed flow rate, the steam ratio
wants to be used as a new feedstock in Olefin 12 unit. and coil outlet temperature. The coded levels and
It was a distilled fraction, 32 °C < bp < 324 °C, with the natural values of the factors are shown in Table 2.
a specific gravity of 0.77. Physicochemical characteristics, The experiments covered the following range of
composition and mean molecular weight are presented variables: temperature; 750- 900°C, and feed flow rate;
in Table 1. 3 - 7 g/min and steam ratio; 0.5-1.4 g/g.

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Iran. J. Chem. Chem. Eng. Olefin Production from Heavy Liquid ... Vol. 29, No. 4, 2010

Table 2: Coded and natural levels of the design factors.

Design factor -1.68 -1 0 +1 1.68

Coil outlet temperature 750 780 825 869 900

Feed flow rate (g/min) 3.0 3.8 5.0 6.2 7.0

Steam ratio (g/g) 0.5 0.68 0.95 1.22 1.4

Exchanger

Exchanger

condensate Water condensate

Fig. 1: Schematic diagram of the thermal cracking setup.

Eight response variables concerned including product MATHEMATICAL MODEL


yield of the main primary products (wt %). Results of Reactor model
the experiments and the design matrix are shown in Table 3. A one-dimensional plug flow model is used
The Relative Absolute Error (RAE), between predicted to simulate the reactor of thermal cracking setup. The set of
and experimental data for every output data of models continuity equations for the process gas species is solved
simultaneously with the energy, momentum equations [11, 12].
was defined as an objective function (Eq. (1)).
These equations are as follows:
Mass balance:
Yexperimental − Ypredicted dFj πd 2t
RAE =
Yexperimental
(1)
dz
( i
s ij r )
ri
4
(2)

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Iran. J. Chem. Chem. Eng. Sedighi M. et al. Vol. 29, No. 4, 2010

Table 3: Design matrix and results of the central composite design.


Run 1 2 3 4 5 6 7 8 9
COT(°C) 750 900 869 780 825 869 869 780 825
Feed flow rate
5 5 6.2 6.2 5 3.8 6.2 3.8 5
(g/min)
Steam ratio (g/g) 0.95 0.95 1.22 0.68 0.95 0.68 0.68 0.68 0.95

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

H2 0.9 1.43 1.31 0.89 1.18 1.4 1.33 0.95 1.2


C5+ 40.18 29.72 29.23 43.09 31.06 27.9 28.73 41.1 31.26

Run 10 11 12 13 14 15 16 17

COT(°C) 780 869 825 825 825 825 780 825


Feed flow rate (g/min) 3.8 3.8 5 7 3 5 6.2 5

Steam ratio (g/g) 1.22 1.22 0.5 0.95 0.95 0.95 1.22 1.4

Experimental Data132.8

CH4 9.67 15.94 12.76 10.7 15.32 13.28 8.6 14.8

C2H6 3.45 2.06 2.61 1.97 2.69 2.19 2.51 2.17

C2H4 21.73 30.37 24.74 23.45 28.4 25.07 191 26.12


C3H8 1.14 0.83 1.42 1.63 0.84 1.28 1.4 1.2
C3H6 13.38 10.62 13.71 15.37 13.49 14.55 14.17 15.12
C4H8 3.4 0.9 2.49 2.93 2.15 2.24 3.52 2.1

H2 0.92 1.37 1.26 1.15 1.37 1.21 0.87 0.99


C5+ 39.52 28.12 31.9 33.87 28.15 31.87 42.19 30.61

Energy balance: Re −0.2 ζ


Fr = 0.092 + (5)
dt πR b
dT πd 2t
FC
j j pj
= Q ( z ) πd t + r
i ri
( −∆H )i (3)
dz 4 and for the tube bends as

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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Iran. J. Chem. Chem. Eng. Olefin Production from Heavy Liquid ... Vol. 29, No. 4, 2010

Kinetic model RT = 0.17s, SR = 1.24 g/g


There are three kinds of model to state kinetic model
50
which are empirical, molecular, and mechanistic models. (a)
Due to the flexibility and accuracy, mechanistic radical 40
kinetic models were widely accepted for thermal cracking

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)

4- Secondary reaction, for example: T = 840 °C, T = 0.17 s


a) C3H6 + H0 C3H50 + H2 50
0 (c)
b)C2H4 + H C2H50
40
Yield (we%)

• Molecular reaction 30
1- Olefin isomerization, for example:
1-C6H110 2-C6H110 20

2- Dehydrogenation reaction, for example: 10


C3H8 C3H6 + H2
0
0.5 0.7 0.9 1.1 1.3 1.5
3- Diels – Alder Molecular reaction, for example:
C4H6 + C2H4 C6H6 + 2H2 Steam ration (g/g)

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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Iran. J. Chem. Chem. Eng. Sedighi M. et al. Vol. 29, No. 4, 2010

Table 4: Comparison of simulated and experimental product distributions.

Test 1 Test 2 Test 3

Parameter Experiment model Experiment model Experiment model

COT(°C) 830 830 885 885 765 765

Feed flow rate(g/min) 5.1 5.1 6.5 6.5 4.1 4.1

Steam ratio (g/g) 0.7 0.7 1.15 1.15 0.9 0.9

Yield (wt %)

CH4 14 12.57 15.4 14.6 9.22 8.53

C2H6 2.14 2.1 1.8 1.91 3.00 2.87

C2H4 26.9 24.8 28.2 30.2 19.7 20.34

C3H6 14 14.54 9.65 9.35 13.41 14.06

C5+ 32.7 34.6 31.9 33.6 41.3 43.7

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.

To avoid complexity in reaction network, the detected RESULTS AND DISCUSSION


species of heavy liquid hydrocarbon were lumped to four The effect of temperature, Residence Time (RT) and
pseudo components as n-C9H20 and i-C9H20 for normal Steam Ratio (SR) on product distribution of ethylene,
paraffins and iso paraffins, C9H18 for naphthenes, and propylene and C5+ is shown in Fig. 2. As shown in Fig. 2(a),
C10H14 for aromatics. Based on pseudo components, increasing the temperature improves the ethylene yield.
reaction network includes 148 reactions for 43 species. The main part of C5+ is untreated feed. By increasing
The developed reaction network is presented in Table 5 the temperature, the conversion increases which leads to
Due to differences between radicals and molecules the sharp decline in the yield of C5+ and increase in the yield
concentrations, the governing mass, energy and momentum of ethylene as shown in Fig. 2(a). The yield of propylene
balance equations can be solved with Gear method. increases slightly and reaches a maximum and then

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Iran. J. Chem. Chem. Eng. Olefin Production from Heavy Liquid ... Vol. 29, No. 4, 2010

The main product yields vs. the length of the reactor


30 are shown in Fig. 5. In general, the yields of ethylene,
25 methane, ethane and hydrogen products increase continuously
along the reactor. Due to the secondary reactions
20 the yield of propylene increases and reaches a maximum
Yield (%)

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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Iran. J. Chem. Chem. Eng. Sedighi M. et al. Vol. 29, No. 4, 2010

Table 5: The developed reaction network.


Parameters Adopted
Reaction
No. LOG (A)1 E2

1. Paraffin → Radical + Radical


1 C9H20 → C5H11 + 1-C4H9 14.5 80.0

2 C9H20 → C6H13 + 1-C3H7 14.5 80.0

3 C9H20 → C7H15 + C2H5 14.5 80.0

4 C9H20 → C8H17 + CH3 14.5 80.0

5 C9H20 → C9H19 + H 14.5 85.0

6 i-C9H20 → CH3 + i-C8H17 14.5 80.0

7 i-C9H20 → C2H5 + i-C7H15 14.5 80.0

8 i-C9H20 → 1-C3H7 + i-C6H13 14.5 80.0

9 i-C9H20 → 1-C4H9 + i-C5H11 14.5 80.0

10 i-C9H20 → i-C4H9 + C5H11 14.5 80.0

11 i-C9H20 → 2-C3H7 + C6H13 14.5 80.0

12 i-C9H20 → H + i-C9H19 14.5 83.0

13 C9H18 → 1-C4H7 + C5H11 14.0 75.0

2. Radical → Radical + Radical


14 C9H19 → C2H4 + C7H15 13.2 30.0

15 C9H19 → C3H6 + C6H13 13.0 30.0

16 C9H19 → 1-C4H8 + C5H11 12.6 29.0

17 C9H19 → C5H10 + 1- C4H9 13.0 35.0

18 C8H17 → C2H4 + C6H13 13.4 31.0

19 C8H17 → C3H6 + C5H11 13.3 30.0

20 C8H17 → 1-C4H8 + 1-C4H9 12.6 29.0

21 C8H17 → C5H10 + 1-C3H7 14.0 32.5

22 C7H15 → C2H4 + C5H11 13.6 45.0

23 C7H15 → C3H6 + C4H9 13.3 31.0

24 C7H15 → 1-C4H8 + 1-C3H7 13.0 29.0

25 C7H15 → C5H10 + C2H5 14.1 32.5

26 C6H13 → C2H4 + 1-C4H9 13.4 30.0

27 C6H13 → C3H6 + 1-C3H7 13.2 29.0

28 C6H13 → 1-C4H8 + C2H5 12.6 31.0


-1 -1 -1
1. Unit of A is: s or L mol s
2. Unit of E is: kCal / mol

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Iran. J. Chem. Chem. Eng. Olefin Production from Heavy Liquid ... Vol. 29, No. 4, 2010

Table 5 (Continued)

Parameters Adopted
No.
Reaction
LOG (A)1 E2

29 C6H13 → C5H10 + CH3 14.0 32.5

30 1-C4H7 → C4H6 + H 11.0 49.3

31 1-C4H7 → C2H4 + C2H3 14.1 39.0

32 C5H11 → C2H4 + 1-C3H7 13.5 28.4

33 C5H11 → C3H6 + C2H5 13.7 38.0

34 C5H11 → C4H8 + CH3 13.5 31.5

35 C5H11 → C5H10 + H 13.7 38.6

36 1-C4H9 → C2H4 + C2H5 12.2 29.0

37 1-C4H9 → C3H6 + CH3 13.3 34.0

38 1-C4H9 → 1-C4H8 + H 13.0 36.6

39 2-C3H7 → C3H6 + H 13.3 38.7

40 1-C3H7 → C2H4 + CH3 13.6 32.6

41 1-C3H70 → C3H6 + H0 13.3 38.4

42 C2H3 → C2H2 + H 9.3 31.5

43 i-C9H19 → C2H4 + i-C7H15 13.1 32.5

44 i-C9H19 → C3H6 + i-C6H13 12.5 30.0

45 i-C9H19 → C3H6 + C6H13 13.1 32.0

46 i-C9H19 → 1-C4H8 + i-C5H11 12.8 30.0

47 i-C9H19 → i-C4H8 + C5H11 13.0 29.0

48 i-C9H19 → C5H10 + i-C4H9 13.5 31.0

49 i-C8H17 → C2H4 + i-C6H13 13.2 32.0

50 i-C8H17 → C3H6 + i-C5H11 13.3 31.0

51 i-C8H17 → C3H6 + C5H11 13.3 30.0

52 i-C8H17 → 1-C4H8 + i-C4H9 12.5 30.0

53 i-C8H17 → i-C4H8 + 1-C4H9 12.5 31.0

54 i-C8H17 → C5H10 + 2-C3H7 13.5 30.1

55 i-C7H15 → C2H4 + i-C5H11 13.5 43.0

56 i-C7H15 → C3H6 + i-C4H9 13.1 30.0

57 i-C7H15 → C3H6 + 1-C4H9 13.0 32.5

58 i-C7H15 → 1-C4H8 + 2-C3H7 13.0 29.5

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Iran. J. Chem. Chem. Eng. Sedighi M. et al. Vol. 29, No. 4, 2010

Table 5 (Continued)
Parameters Adopted
No. Reaction
LOG (A)1 E2

59 i-C7H15 → i-C4H8 + 1-C3H7 12.5 31.0

60 i-C6H13 → C2H4 + i-C4H9 13.2 31.0

61 i-C6H13 → C3H6 + 2-C3H7 13.4 31.0

62 i-C6H13 → C3H6 + 1-C3H7 13.1 29.0

63 i-C6H13 → i-C4H8 + C2H5 13.4 32.5

64 i-C5H11 → C2H4 + 2-C3H7 13.0 29.0

65 i-C5H11 → C3H6 + C2H5 13.1 31.0

66 i-C5H11 → 1-C4H8 + CH3 13.7 32.8

67 i-C5H11 → i-C4H8 + CH3 13.0 30.0

68 i-C4H9 → C3H6 + CH3 14.0 32.8

69 i-C4H9 → i-C4H8 + H 13.5 30.0

70 i-C4H9 → 2-C4H8 + H 13.0 30.2

3. Paraffin + Radical → Paraffin + Radical


71 C9H20 + H → C9H19 + H2 12.0 15.0

72 C9H20 + CH3 → C9H19 + CH4 11.5 9.5

73 C9H20 + C2H5 → C9H19 + C2H6 11.6 10.0

74 C9H20 + 1-C3H7 → C9H19 + C3H8 11.1 11.0

75 C9H20 + C2H3 → C9H19 + C2H4 11.5 9.0

76 i-C9H20 + H → H2 + i-C9H19 11.0 12.5

77 i-C9H20 + CH3 → CH4 + i-C9H19 11.5 9.0

78 i-C9H20 + C2H3 → C2H4 + i-C9H19 12.0 9.5

79 i-C9H20 + C2H5 → C2H6 + i-C9H19 11.1 10.0

80 i-C9H20 + 1-C3H7 → C3H8 + i-C9H19 10.1 9.0

81 i-C9H20 + 2-C3H7 → C3H8 + i-C9H19 10.5 8.0

82 C3H8 + H → 1-C3H7 + H2 10.5 9.7

83 C3H8 + CH3 → 1-C3H7 + CH4 9.0 12.5

84 C3H8 + C2H5 → 1-C3H7 + C2H6 8.5 12.3


85 11.1 10.5
C2H6 + H → C2H5 + H2
86 11.6 16.5
C2H6 + CH3 → C2H5 + CH4
87 8.0 10.0
C2H6 + 1-C3H7 → C2H5 + C3H8
88 11.5 12.5
CH4 + H → CH3 + H2

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Iran. J. Chem. Chem. Eng. Olefin Production from Heavy Liquid ... Vol. 29, No. 4, 2010

Table 5 (Continued)
Parameters Adopted
No. Reaction
LOG (A)1 E2

89 CH4 + C2H5 → CH3 + C2H6 7.0 11.0

90 CH4 + 1-C3H7 → CH3 + C3H8 8.3 18.0

91 H2 + CH3 → H + CH4 8.9 10.9

92 H2 + C2H5 → H + C2H6 9.5 13.0

93 H2 + 1-C3H7 → H + C3H8 9.0 15.6

94 H2 + 2-C3H7 → H + C3H8 9.5 15.0

95 H2 + C3H5 → H + C3H6
0
10.5 20.0

96 H2 + 1-C4H9 → H + C4H10 9.5 16.5

97 H2 + 2-C4H9 → H + C4H10 9.7 17.5

98 H2 + i-C4H9 → H + C4H10 9.5 16.5

99 C2H6 + 1-C4H9 → C2H5 + C4H10 8.5 12.5

100 C2H6 + 2-C4H9 → C2H5 + C4H10 8.0 12.9

101 C2H6 + i-C4H9 0


→ C2H5 + i-C4H10 8.5 12.5

4. Radical + Radical → Paraffin


102 1-C3H7 + H → C3H8 11.0 0

103 C2H5 + H → C2H6 11.5 0

104 2-C3H7 + H → C3H8 11.0 0

105 1-C4H9 + H → C4H10 11.0 0

106 i-C4H9 + H → i-C4H10 11.0 0

107 C5H11 + H → C5H12 11.0 0

108 2-C3H7 + CH3 → i-C4H10 10.3 0

109 C6H13 + H → C6H14 11.0 0

110 CH3 + CH3 → C2H6 11.3 0

5. Secondary Reaction I; Olefin + Radical → Paraffin + Olefinic Radical


111 C3H6 + H → C3H5 + H2 10.7 5.0

112 C3H6 + CH3 → C3H5 + CH4 7.5 8.0

113 C3H6 + C2H5 → C3H5 + C2H6 8.0 10.5

114 C3H8 + C3H5 → C3H6 + 1-C3H7 9.0 20.5

115 1-C4H8 + H → C4H7 + H2 11.0 5.0

116 1-C4H8 + CH3 → C4H7 + CH4 8.0 7.3

117 1-C4H8 + C2H5 → C4H7 + C2H6 8.0 8.3

118 C3H8 + C4H7 → C4H8 + 1-C3H7 9.69 6.0

145
Iran. J. Chem. Chem. Eng. Sedighi M. et al. Vol. 29, No. 4, 2010

Table 5 (Continued)
Parameters Adopted
No. Reaction
LOG (A)1 E2

119 C5H10 + H 0
→ C5H9 + H2 12.0 8.0

120 C5H10 + CH3 → C5H9 + CH4 9.7 12.5

121 C5H10 + C2H5 → C5H9 + C2H6 9.6 14.5

122 C3H8 + C5H9 → C5H10 + 1-C3H7 9.69 16.0

6. Secondary Reaction II

123 C2H4 + H → C2H3 + H2 8.9 4.0

124 C2H4 + CH3 → C2H3 + CH4 10.0 12.0

125 C2H4 + C2H5 → C2H3 + C2H6 9.4 25.0

126 C2H4 + H → C2H5 9.9 1.5

127 C2H4 + CH3 → 1-C3H7 8.6 7.9

128 C2H4 + C2H5 → 1-C4H9 7.8 7.6

129 C2H4 + C2H3 → C4H6 + H 11.0 50.0

130 C2H4 + C2H3 → C4H7 7.7 5.5

131 C3H6 + H → 1-C3H7 10.1 3.0

132 C3H6 + CH3 → 1-C4H9 8.5 7.4

133 1-C4H8 + H0 → 1-C4H9 9.9 1.2

134 1-C4H8 + CH3 → C5H11 8.3 7.2

7. Molecular Reaction I

135 C3H8 → C3H6 + H2 12.0 50.0

136 C4H6 + C2H4 → C6H6 + 2H2 9.9 34.6

137 C4H6 + C3H6 → C7H8 + 2H2 9.0 35.6

138 C4H6 + 1-C4H8 → C8H10 + 2H2 14.8 60.0

139 C4H6 + C4H6 → C8H8 + 2H2 9.2 29.8

8. Molecular Reaction II 7

140 4C6H6 → 3(C4H)X + 9H2 15.3 50.7

141 4C7H8 → 7(C4H)X + 12.5 H2 15.3 50.7

142 C8H10 → 2(C4H)X + 4H2 15.3 50.7

143 C8H8 → 2(C4H)X + 3H2 15.3 50.7

144 2C2H6 → C3H8 + CH4 12.5 65.0

145 C3H6 + C2H6 → C4H8 + CH4 14.0 60.0

146 C3H8 → C2H4 + CH4 10.6 50.0

147 C3H8 → C3H6 + H2 10.7 51.0

148 2C3H6 → 3C2H4 12.8 64.0

146
Iran. J. Chem. Chem. Eng. Olefin Production from Heavy Liquid ... Vol. 29, No. 4, 2010

REFERENCES Thermal Cracking for Olefin Production, Korean J.


[1] Pinter A., Tungler A., Nagy L., Vida L., Kovacs I., Chem. Eng., 23, p. 8 (2006).
Kerezsi J., A Laboratory Steam-Cracking Reactor [13] Ranzi E., Dente M., Goldaniga A., Bozzano G.,
to Characterize Raw Materials, International Journal Faravelli T., Lumping Procedures in Detailed
of Chemical Reactor Engineering, 2, A15 (2004). Kinetic Modeling of Gasification, Pyrolysis, Partial
[2] Hirato M., Yoshioka S., Matanuska Thermal Cracking Oxidation and Combustion of Hydrocarbon Mixtures,
of Gas Oil, Naphtha and Kerosene for Production of Progress in Energy and Combustion Science, 27,
Light Olefins, Hitachi Rev, 20, 326 (1971). p. 99 (2001).
[3] Belohlav Z., Zamostny P., Herink T., The Kinetic [14] Sundaram K.M., Froment G., Modeling of Thermal
Model of Thermal Cracking for Olefins Production, Cracking Kinetics. 3. Radical Mechanisms for the
Chemical Engineering and Processing, 42, p. 461 Pyrolysis of Simple Paraffins, Olefins, and Their
(2003). Mixtures, Ind. Eng. Chem. Fund., 17, p. 174 (1978).
[4] Ghassabzadeh H., Towfighi Darian J., Zaheri P., [15] Dente, M., Ranzi, E. and Goossens, A.G., Detail
Experimental Study and Kinetic Modeling of Prediction of Olefin Yields from Hydrocarbon
Kerosene Thermal Cracking, J. Anal. Appl. Pyrolysis, Pyrolysis through a Fundamental Simulation Model
86, p. 221 (2009). (SPYRO), Comput. Chem. Eng., 3, p. 61 (1979).
[5] Depeyre D., Flicoteaux C., Arbabzadeh F., [16] Froment G., Van de Steene, B.O. and Van Damme,
Zabaniotou, A., Modeling of Thermal Steam P., Thermal Cracking of Ethane and Ethane-Propane
Cracking of an Atmospheric Gas Oil, Ind. Eng. Mixtures, Ind. Eng. Chem. Process Des. Dev., 15,
Chem. Res. 28, p. 967 (1989). p. 495 (1976).
[6] Zahedi S., Towfighi J., Karimzadeh R., Omidkhah M.,
Determination of Yield Distribution in Olefin
Production by Thermal Cracking of Atmospheric
Gasoline, Korean J. Chem. Eng., 24, p. 681 (2008).
[7] Keyvanloo K., Towfighi J., Sadrameli S.M.,
Mohamadalizadeh A., Investigating the Effect of
Key Factors, Their Interactions and Optimization of
Naphtha Steam Cracking by Statistical Design of
Experiments, J. Anal. Appl. Pyrolysis, 87, p. 224
(2010).
[8] Poustma M.L., Fundamental Reactions of Free
Radicals Relevant to Pyrolysis Reactions, J. Anal.
Appl. Pyrol., 54, p. 5 (2000).
[9] Franz J.A., Camaioni D.M., Autrey T., Linehan J.C.,
Alnajjar M.S., Measurement of Select Radical
Processes in Hydrocarbon Pyrolysis, J. Anal. Appl.
Pyrol., 54, p. 37 (2000).
[10] Safarik I., Strausz O.P., The Thermal Decomposition
of Hydrocarbons. Part 3. Polycyclic n-Alkylaromatic
Compounds, Res. Chem. Intermed., 23, p. 179 (1997).
[11] Sadrameli S.M., Green A.E.S., Systematics and
Modeling Representations of Naphtha Thermal
Cracking for Olefin Production, J. Anal. Appl.
Pyrolysis, 73, p. 305 (2005).
[12] Towfighi J., Niaei A., Karimzadeh R., Saedi G.,
Systematics and Modelling Representations of LPG

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