174 Ind. Eng. Chem. Fundam., Vol. 17, No.

3, 1978

Literature Cited Rasquin, E. A., Lynn, S., Hanson, D. N., Ind. Eng. Chem. Fundam., 16, 103
(1977).
Beychok. M. R., "Coal Gasification and the Phenosolvan Process", presented Sherwood, T, K,, ~ , A,
~ L,, T l ~ i ~lnst, Chem,
~~ ~ ,~36,39-7~
~ ~
at the 168th National Meeting of the American Chemical Society, Atlantic (1940).
City, N.J., 1974. Wurm, H.J., Gluckauf, 104 (12),517 (1968).
Earhart, J. P., Ph.D. Thesis, University of California, Berkeley, Calif., 1975.
Leva. M., Chem. Eng. Prog. Symp. Ser., 50 (lo),51 (1954).
Mulligan, T. J., Fox, R. D.,Chem. fng., 83 (22),49 (1976).
Newman, J., Ind. Eng. Chem. Fundam., 7 , 314 (1968). Received f o r review April 11,1977
Rasquin, E. A., M. S. Thesis, University of California, Berkeley, Calif., 1977. Accepted April 20,1978

Modeling of Thermal Cracking Kinetics. 3. Radical Mechanisms

for the Pyrolysis of Simple Paraffins, Olefins,
and Their Mixtures
K. Meenakshi Sundaram and Gllbert F. Froment'
Laboratorium voor Petrochemische Techniek, Rijksuniversiteit, Gent, Belgium

Radical reaction schemes for the cracking of ethane, propane, normal and isobutane, ethylene, and propylene
were set up. The kinetic parameters of these schemes were determined by fitting experimental data obtained
under nonisothermaland nonisobaric conditions in a pilot plant. The set of continuity equations for both molecu-
lar and radical species was integratedusing Gear's algorithm for stiff differential equations. The reliability of the
parameters was tested by simulating the cracking of binary and ternary paraffinic mixtures. A satisfactory fit of
the results of mixtures cracking was obtained with a reaction scheme derived from the superposition of the
schemes for single-component cracking.

Introduction gas temperature and total pressure profiles. It is assumed that

Thermal cracking reactions mainly proceed via free radical
mechanisms (Laidler, 1965). Many specific mechanisms have
been proposed to explain the cracking of simple molecules.
The majority of the mechanisms have been deduced from data
obtained at subatmospheric pressures, low temperatures, and
low conversions. Moreover, they were derived through the
pseudo-steady-stateconcept which assumes the radical con-
centrations to be constant. This condition is not fulfilled in
reality, neither in an industrial reactor nor even in an iso-
thermal bench scale reactor (Edelson and Allara, 1973). For
these reasons, at elevated temperatures the uncertainties in
the parameters are high and sometimes attain orders of
magnitude. In the present paper radical schemes for the
cracking of normal and isoparaffins, olefins, and their mix-
tures are developed. The determination of their kinetic pa-
rameters is based upon experiments conducted in a pilot re-
actor under conditions as close as possible to those used in
industry (Van Damme et al., 1975; Froment et al., 1976a,b,
1977).
Continuity Equations
Free radical reactions involve initiation, propagation or
H-abstraction, and termination steps. The continuity equa-
tion for t h e j t h species in an isothermal reactor with plug flow
may be written
d F, N adopted in this work. Gear's method can be applied to any
= -0Rj = -0 ,E (sijri)
dz 1-1
For nonisothermal and nonisobaric conditions the reaction
rate ri has to be computed for the experimentally measured
0019-7874/78/1017-0174$01.00/0
the reactions are elementary and therefore the order corre-
sponds to the molecularity. Also, the rate coefficients obey the
Arrhenius relationship within the temperature range cov-
ered.
The first-order differential equations represented by eq 1
are usually nonlinear and coupled, and hence analytical so-
lutions are not possible. The concentrations of the radicals are
much lower than those of the molecular species (e.g., vs.
10-2 M) so that the eigenvalues of the differential equations
differ by orders of magnitude. With classical integration
methods, an extremely small step size has to be used to ensure
the stability of the numerical integration. To overcome the
mathematical difficulties, pseudo-steady state for radical
concentration has been assumed. This assumption allows the
differential equations for the radicals to be replaced by alge-
braic equations (Snow, 1966; Pacey and Purnell, 1972b;
Blakemore and Corcoran, 1969). In a recent communication
the present authors (to be published) have quantified the
errors induced by this assumption and shown that for reliable
parameter estimates, the complete integration for the conti-
nuity equations for both molecular and radical species for the
entire conversion range is essential, because the radicals vary
significantly and continuously with conversion.
Of the many currently available methods for integration of
stiff differential equations (see Aiken and Lapidus, 1974,
1975a,b; Seinfeld et al., 1970; Sena and Kershenbaum, 1975a1,
the one proposed by Gear (1971) seems to emerge. It is also
degree of stiffness and allows for any degree of accuracy of
integration with moderate computer time. It essentially uses
the Adams-Moulten predictor-corrector method, which is an
implicit technique.
0 1978 American Chemical Society

Experimental D a t a
The pilot reactor details and the experimental results used
in this work have been reported already by Van Damme et al.
(1975) and Froment et al. (1976a,b, 1977). Briefly, the results
cover an outlet pressure of 1.2 to 2.2 atm abs with dilution
factors ranging from 0.35 to 1.2 kg of steamkg of hydrocarbon.
The outlet temperatures varied from 650 to 860 "C, depending
upon the species cracked and the conversion level. The pres-
sure drop varied from 0.3 to 0.5 atm and the Reynolds number
from 5000 to 10 000.
General R e m a r k s Concerning the Reaction Scheme
In this work only the major reactions and a fraction of the
minor reactions reported in the literature will be considered.
The experimental product distribution is used as a guideline
to limit the number of reactions. Recently, Sena and Ker-
shenbaum (197513) proposed a method to discriminate be-
tween several possible radical mechanisms using the con-
straints imposed by stoichiometry and kinetics. Such a tech-
nique is useful for a small number of reactions only and is not
applicable here.
In each reaction scheme all the important radicals are
considered, although all the products heavier than C5H10 have
been lumped as a single component, C5+. Radicals heavier
than C5H11- are not considered. Aromatic and naphthenic
radicals and species are left out, for lack of relevant kinetic
data. The pyrolysis of aromatic substances mainly yields coke
and small molecules such as hydrogen and methane (Kinney
and Delbel, 1954). For each radical at least one termination
is considered. The pyrolysis is taken to be homogeneous;
heterogeneous reactions on the wall are not considered.
The complete reaction scheme is shown in Table I. The
reactions to be selected in the simulation of the individual
cracking of the paraffins and olefins considered here are shown
in Table 11. Inclusion of molecular reactions was found to be
necessary, a t least for olefin cracking. Each case is discussed
separately in subsequent sections.
Selection of P a r a m e t e r s
Rate constants for several hundred reactions carried out
a t low temperatures were recently compiled by Allara (per-
sonal communication). Rate constants for metathetical re-
actions of atoms and radicals have been reviewed recently by
Kerr (1976) and earlier by Trotmann-Dickenson (1965). Rate
constants for addition reactions are dealt with by Abbe1
(1976). Kunugi et al. (1969,1970) tabulated rate constants for
many reactions of olefin cracking. The majority ofthe studies
available in the literature are limited to low temperatures and
low pressures, however. For satisfactory prediction at the high
temperatures encountered in this work, adaptation of the
frequency factor and/or activation energy was found to be
necessary. Initially in this work the experiments were reduced
to isothermality using the equivalent reactor volume concept
(Hougen and Watson, 1947), discussed in detail by Froment
et al. (1976a) and Van Damme et al. (1975).
A set of parameters which can satisfactorily explain the
observed product distribution at various conversions and
temperatures was found by trial and error. However, when
such parameters were applied to simulate unreduced non-
isothermal and nonisobaric data, significant discrepancies
between the experimental and calculated product distribu-
tions sometimes of the order of 100% were observed. This is
not so surprising, since the equivalent reactor volume concept
is strictly valid only for a single reaction or for a set of parallel
reactions with identical activation energy. In radical reactions
the activation energy varies from 0 kcal/mol for terminations
to 80-100 kcal/mol for initiations, and hence it is not possible
to get a unique equivalent reactor volume valid for all the re-
Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978 175
actions, It was therefore decided to deal with the data as ob-
tained, that is to account for the temperature and pressure
profile in the simulations required to determine the best
values of the parameters.
In the previous papers dealing with molecular models the
parameters were estimated by nonlinear regression (Sunda-
ram and Froment, 1977).Due to the large number of reactions
this technique could not be applied here, so that the param-
eters were obtained by ordinary trial and error. I t should be
added that unique values were selected for the parameters of
reactions occurring in more than one cracking. The most re-
liable values of the parameters of such a reaction are of course
obtained from that cracking in which the reaction is most
abundant. Therefore, the final set of parameter values was
only obtained through an iteration loop involving the data on
the cracking of all the substances, superimposed upon the
iteration loop dealing with the cracking of one hydrocarbon
only.
Finally all the reactions were added up to one large model
which was found to be valid for mixture cracking too, without
any further adaptation.
E t h a n e Cracking
Ethane cracking has been studied by many workers. Simple
reaction schemes involving 6 to 1 2 reactions have been pro-
posed (Pacey and Purnell, 1972b; Snow, 1966; Lin and Back,
1966a,b;Bradley and Frend, 1971). In the present work a total
of 49 reactions, given in Table 11, were considered to be nec-
essary to cover the range of conversions of practical impor-
tance. The reaction scheme accounts for 20 species (11mo-
lecular and 9 radical) which are also mentioned in Table 11.
The radical concentrations along the reactor are shown in
Figure 1, for a typical experimental temperature profile. The
calculated conversion profile is also shown in Figure 1.The
radical concentrations for some radicals like 1-C4Hg0do not
change very much beyond 30% of the reactor length, although
the temperature varies from 750 to 850 "C. Major radicals such
as H- and CH3. vary significantly, however. Even under iso-
thermal conditions they never attain steady state (Sundaram
and Froment, to be published). Concentration profiles of
hydrogen and methane are also shown in the same figure for
comparison. It can be seen that the concentrations of molec-
ular and radical species differ by more than seven orders of
magnitude.
The calculated and experimental product distributions for
some of the major products are shown in Figure 2 as a function
of ethane conversion. The agreement is excellent a t all con-
version levels.
It is found that an increase in the rate of the initiation
leading to methyl radicals has a more pronounced effect on
the C5+ yield than on the ethane conversion. The latter is
much more favored by an increase in the rate of propaga-
tion
C2Hs + Ha - CzH5. + H2
The decomposition of the ethyl radical into ethylene and
H.
not only affects the product distribution but also the overall
kinetics.
I t has been argued that under normal pyrolytic conditions
the latter reaction operates in its pressure-dependent region
(Pacey and Purnell, 1972b;Blakemore et al., 1973).The results
are uncertain, however, and due to lack of sufficient infor-
mation first order is adopted here with the kinetic parameters
recommended by Allara (personal communication). High
selectivities for methane are observed at high temperatures
176 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978

Table I. Reaction Scheme for the Pyrolysis of Paraffins and Olefins

A, A,
s-lorL E, s-1orL E,
no. reaction mol-' s-' kcal/mol source no. reaction mol-' 5-l kcal/mol source
1.
2.
4.0 X
2.0 x
10l6
10'6
87.5
84.5
a
a
+
41. CzH4 CzH5-
C~HG
- CHy + 3.0 x 109 19.0 e

3. 1.5 X 10l6 82.1 a 42. 1.0 x 108 9.2 d

4. 9.0 x 10'6 85.4 a
43. 1.2 x 109 12.6 a
5. 2.0 x 10'6 82.0 a
44. 8.0 X lo8 10.4 a
6. 9.0 x 1013 65.0 a
7. 8.0 x 1017 95.0 a 45. 2.0 x 108 8.3 a
8. 3.5 x 10'6 86.0 a
9. 3.5 x 10" 51 0 a 46. 6.0 x 107 8.3 a

10. 8.0 X 1OI6 14.0 b 47. 2.0 x 109 12.6 a

11. 2.0 x 10'6 71.3 a
12. 8.0 X lo8 4.0 a 48. 4.5 x 108 10.4 a
13. 1.0 x 10" 9.7 a
14. 2.5 x 109 1.1 C 49. 1.5 x 109 10.4 a
15. 1.0 x 10" 9.7 a
50. 1.0x 109 18.8 d
16. 9.0 x 1010 8.3 a
51. 8.0 X lo8 16.2 d
17. 5.0 X 1O1O 3.9 d
52. 2.0 x 108 13.5 a
18. 5.0 X 1O1O 3.8 a
53. 4.0 X lo8 18.8 d
19. 3.0 X 1O1O 3.8 a
54. 8.0 X lo8 16.8 d
20. 1.5 X 10" 9.7 a
55. 1.0x 109 19.0 a
21. 9.0 x 1010 8.4 a
56. 1.0 x 108 9.2 d
22. 1.0 x 10'1 8.4 a
57. 1.0 x 108 10.2 d
23. 1.0 x 10'0 13.0 a
58. 2.0 x 108 10.4 a
24. 3.8 X 10" 16.5 a
59. 2.0 x 108 12.6 a
25. 2.0 x 109 12.2 a
60. 1.0 x 108 13.4 a
26. 3.4 x 1010 11.5 a
61. 2.0 x 109 31.5 a
21. 4.0 x 109 10.1 a 62. 3.2 x 1013 40.0 d
+
CH4
+
28. l-C4H8 CHy - C4H7. 1.0 x 108 7.3 d
63.
64.
3.0 X
4.0 x
1O'O
1013
36.2
32.6
a
d
+
CH4
+
29. 2-C4H8 C H r - C4H7. 1.0 x 108 8.2 a
65. 2.0 x
2.0 x
1013
1013
38.4
38.1
d
a
+
CH4
+
30. i-C4H8 C H r - Me 3.0 X lo8 7.3 a
67.
68.
1.2 x 1014
1.0 x 101'
49.3
37.0
d
a
+
allyl CH4
+
31. n-C4Hlo CHy - 1- 3.5 x 10'0 11.6 a
69.
70.
1.0x 1013 32.6
28.0
a
a
+
C4H9' CH4
32. n-C4Hlo + CHy
+
- 2- 3.5 x 109 9.5 a
71.
72.
28.0
36.6
d
d
C4H9' CH4
33. i-CQH10 + CH3.
C4H9' + CH4
- i- 9.5 x 109 9.0 a
73.
74.
75.
31.9
39.8
36.0
d
d
a
+
34. C3H6 CzH3. + C3H5- + 3.0 x 109 14.5 a 76. 33.0 d
77. 36.6 a
35. 3.0 x 109 18.8 a 78. 36.6 d
79. 31.5 D
36. 1.0 x 109 16.2 a 80. 28.7 d

37. 1.0x 109 13.0 a 81. 1.3 a

82. 1.5 d
38. 1.0x 109 18.0 a 83. 1.5 a
84. 2.9 d
39. 8.0 X lo8 16.8 a 85. 1.5 f
86. 1.3 g
40. 1.0x 109 16.8 a 87.
88. 2-C;Hi + H. - 2-C;Hg- 6.3 X lo9
1.2
1.2
d
d
 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978 177

Table I (continued)

A, A,
s-lorL E, s-lorL E,

-
no. reaction mol-' s-l kcal/mol source no. reaction mol-' kcal/mol source
89. 1.0 x 10'0 1.2 a 115. 1-C3H7-+ C H r n- 3.2 X lo9 0 a
90.
91.
2.0 x 108
1.5 X lo8
7.9
7.4
a
a
C4H10
116. 2-C3H7*+ CH3. n - - 3.2 X lo9 0 a
92.
93.
94.
3.2 X lo8
3.2 X lo8
1.0 x 108
7.4
9.1
7.2
h
d
a
C4H10
117. C4H7- + C H r C5+0
118. Me allyl CHY +
-- 3.2 X 109
3.2 x 109
0
0
a
a
95. 5.0 x 107 7.0 a c5+
96. 1.5 x 107 7.6 d 119. CzHr CzHy C4H6 + 1.3 X 10" 0 a
97. 1.3 x 107 7.5 d 120. C4H7- + CzHr ---zC5+ 1.3 X 10'0 0 a
98. 2.0 x 107 7.4 d +
121. CzHy C2H.y n- -+ 4.0 X lo8 0 k
C4HlO
99. 1.3 x 107 6.9 d 122. CzHs + C2H.y CzH4 -+ + 5.0 X IO7 0 1
CZH6
100. 5.2 x 1014 41.0 i 123. C3Hy + C2H.y C5+ 3.2 X 109 0 d
+
-+

101. 1.0 x 1010 0 a 124. 1-C3H7' C2H.y -+ 8.0 X lo8 0 d

102.
103.
4.0 X 1Olo
2.0 x 10'0
0
0
i
a
c5+
125. 2-C3H7' C2Hs + - 8.0 X lo8 0 d
104.
105.
106.
1.0 x 10'0
1.0 x 10'0
2.0 x 10'0
0
0
0
d
d
a
c5+
126. C4H7- + C2H.y C5+
127. C3H.y + C3H.y C5+
- 3.2 X 109
3.2 X 109
0
0
d
d
128. C4H7. + C3H5' C5+
-+

107. 2.0 x 10'0 0 a 1.3 X 101" 0 d'

+
-+

108. 1.0 x 10'0 0 d 129. Me allyl C3HS -+ 1.3 X 1O1O 0 a

109. 1.0 x 10'0 0 d c5+
110. 1.0 x 10'0 0 d 130. C4H7*+ C4H7. C5+ 3.2 X 109 0 d
+
-+

111. 1.0 x 10'0 0 d 131. CzHz 2C Hz 5.0 X 10l2 62.0 a

132. CzH4 + Hz CzH6
-
--+

112. 1.3 X 1O1O 0 a -+ 9.2 X lo8 32.8 m

113. 3.2 x 109 0 a 133. CZH4 + C4H6 C6H10 3.0 x lo7 27.5 n
114. 3.2 x 109 0 a
a Estimated by authors. Kunugi et al. (1969). Kunugi et al. (1970). Recommended values by Allara. e Lin and Back (1969a).
f Kurylo et al. (1971). 8 Yang (1962). Cventanovic and Irwin (1967). Lin and Back (196913).j Kurylo et al. (1970). Hiatt and Benson
(1972). Lalonde and Price (1971). Sundaram and Froment (1977). VI Bowley and Steiner (1951). Products heavier than C5H10
are denoted as C5+.

Table 11. Summary of Reaction Schemes for the Pyrolysis of Single Components
total
no.
of
reac-
component tions molecular species radicals reactions considered
ethane 49 Hz= CH4, CzHz, Ha, CHr, CzH3*, 1, 3,4,10, 12, 13,23,24,41,61-65,67,
CZH4, CZH6, C3H6, CZH5.p 68,71,72, 78-82,84,86,90,95-98,
C3H8, C4H6r 1- C3H5', I-C~HT,C~H~~~01-104,106,108,111-114,117,119-122,
. .
C4H8, n-C4HlO9c5+ I-C~HY, C5H11. 126,128; 130; 131
propane 80 Hz, CH4, CzHz, Ha, CH3., CzH3*, 1,2,10,12-17,23-28,34-36,41-44,50,
CZH4, CZH6, C3H6, CZHS, 51,61-68,71-74,78-82,84-87, go, 93,
C3H.9, C4H6,1- C3H5', 1-C3Hyr2- 95-106,108,109,111-117,119-128,130,
C4H8, n-C4HlO, c5+ C3H7', 131
C4H7-,1-C4Hg', 2-
C4H9*,C5Hii-
n-butane 86 same as propane same as propane 1,3,4,10,12-17,20, 21, 23-28,31,32,34,
38,39,41,42,45,47,48,53,54,58,59,
61-68,71-74,78-82,~4-87,go, 92,
95-106,108,109,111-117,119-123,126-128,130,131
5,10-14,17-19,22-25,28-30,33,34,37,
40,42,46,49,52,55-57,60-64,66-70,
73-80,~1-95,97-99,101-107,109-114,
117-120,125,127-131

1,3,4,6, 10,12-14,23-25,34,41,61-68,
71-74,78-82,84-87,90,92,95-97,101-106,108,109,111-114,117,
119-128,130-133
7-10,12-14, 23-25,34,41,42,56,57,
61-68,71-74,78-82,84-87, go, 92,
95-106,108,109,111-117,119,120,
123-126,128,130,131
178 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978
0 10 20 30 LO 50 60 70 80 90 IW
*/a OF REACTOR LENGTH
Figure 1. Calculated concentration of radicals, hydrogen, and
methane and conversion along the reactor for ethane cracking:Po =
2.0 atm abs; 6 = 1.0 kg of steam/kg of ethane; ,. experimental con-
version; lines, calculated.
YIELD YIELD
wt % wt %
50 f !7
Figure 2. Product distribution vs. ethane conversion:Po = 2.0 atm
abs; 6 = 1.0 kg of steam/kg of ethane; points, experimental; lines,
simulated.
(or high conversions) in this work, confirming the results of
Pacey and Purnell(1972a). Methane is formed primarily by
CzH6 + CH3. - CzH5- + CH4
Lin and Back (1966a) used an activation energy of 10.8 kcal/
mol at low temperatures while at high temperatures Pacey and
Purnell found a value of 21.5 kcal/mol. Since the temperature
along the reactor varied from low to high values, a value of 16.5
kcal/mol, combined with a suitably modified frequency factor
satisfactorily predicted the methane yields at all conversions
and temperatures.
Propane Cracking
The low-temperature pyrolysis of propane has been mod-
eled by Allara and Edelson (1975) and by Laidler et al. (1962).
High-temperature cracking has been studied by Buekens and
Froment (1968), Herriott et al. (1972),and Van Damme et al.
(1975).
The importance of the allyl radical in alkane cracking,
especially in propane cracking, has been pointed out by
Buekens and Froment and has been confirmed later by Allara
and Edelson. For this reason the unsaturated radicals CzHy,
C3H5', and C4H7. are also considered in the present model. In
propane cracking, hydrogen, methane, ethane, ethylene, and
propylene are observed as primary products. Small quantities
of acetylene, 1-butene, butadiene, and C5+ are observed a t
high conversions. In the present model a total of 80 reactions
between 11molecular species and 11radical species are con-
sidered (Table 11).
100
-7
-11 0
a (0 2b io ia 6 $0 rb do io
! I
-10
rtc
500
%OF REACTOR LENGTH
Figure 3. Calculated concentration of radicals, ethylene, and pro-
.,
pylene and conversion along the reactor for propane cracking: Po =
2.0 atm abs; 6 = 0.4 kg of steam/kg of propane; propylene content of
the feed, 3 wt %; experimental conversion;lines, calculated.
The formation of primary products has already been dis-
cussed by Buekens and Froment (1968). The main initiation
is
C3H8 - C2Hy + CHy
The probability of 2-C3H7-splitting into C2H4 and CH3- is
extremely low under normal pyrolytic conditions (Leathard
and Purnell, 1970). This radical mainly yields C3H6 and H-,
while C2H4 and CH3. mainly originate from 1-C3H7-.
The formation of acetylene is accounted for by the de-
composition of vinyl radicals which are mainly produced by
metathetical reactions with ethylene (Kunugi et al., 1969;
Benson and Hougen, 1967).
The decomposition of the allyl radical, produced by me-
tathetical reactions with propylene, is also included
C3H5* + C2H2 + CH3.
The decomposition and polymerization of this radical has
been discussed recently by Froment et al. (1976b).
Two possibilities have been considered for the formation
of butadiene. According to Benson and Hougen (1967)
CzH3. -k CzH4 + C4H6 + H.
whereas Kunugi et al. (1969) proposed
C2H3. + CzH4 -+ C4H7-
C4H7' 4 C4H6 + Ha
The second possibility was retained. It should be noted that
the methyl allyl radical or 3-butenyl radical C4H7- exists in
isomeric foms (Beckwith, 1973). No distinction between these
is made here, except for those forms derived from isobutene.
Termination by vinyl, allyl, and methyl allyl radicals is also
considered. Whittle (1972) reports that disproportionation
of allyl radicals is far less abundant than recombination. The
ratio between the two at temperatures ranging from 164 to 190
"C is 0.008. Since termination is nearly independent of tem-
perature, it is assumed that the same ratio holds well at the
normal pyrolytic temperatures and hence only recombination
is retained here. The other unsaturated radicals are treated
in the same manner.
H-transfer reactions involving allyl radicals are important
at high temperatures since the concentration of allyl radicals
is higher than that of any'other radical. This work confirms
the part played by the allyl radical which has been neglected
by most of the workers in alkane pyrolysis.
Computed concentrations of radicals and of a few molecular
species along the reactor are shown in Figure 3, along with the

Figure 4. Product distribution VS. propane conversion: Po = 2.0 atm
abs; 6 = 0.4 kg of steam/kg of propane; points, experimental; lines,
simulated.
Table 111. Comparison of Product Distributions Obtained
by Nonisothermal and by Isothermal Simulations of
Propane Crackinga
yield in wt %
is0 is0
species non-iso (800 "C) (775 "C) exptl
CH4 16.6 16.8 16.8 16.3
C2H4 26.0 26.8 26.4 25/6
C3H6 17.9 17.7 17.8 18.1
C4H6 0.62 0.65 0.6 0.9
c5+ 1.4 1.3 1.4 1.0
a 6 = 0.4 kg/kg; conversion = 66%.
experimental temperature profile. The experimental and
calculated propane conversions are also shown in the same
figure. An example of an isothermal simulation is given else-
where (Sundaram and Froment, to be published). The cal-
culated and experimental product distribution for the major
species are compared in Figure 4. Van Damme et al. (1975)
found that the product distribution is nearly independent of
temperature when plotted vs. the conversion. This is illus-
trated by the comparison of the product distributions given
in Table I11 obtained by nonisothermal simulation and by
isothermal simulations a t two temperature levels. It is of in-
terest to mention here that an isothermal simulation a t 800
O C based upon the pseudo-steady-state approximation yielded
the following product distribution (in wt %) a t 66% conversion:
CH4, 17.3; CzH4, 22.8; C3H6, 14.0; C4H6, 1.2; Csf, 2.4. This
clearly shows that the pseudo-steady-state approximation
leads to errors which are not acceptable.
The overall order for the disappearance of propane is 0.9
a t 50% conversion and 775 "C and 1.08 a t 65% conversion and
800 "C which is close to the first-order experimentally found
by Van Damme et al. (1975) and by Buekens and Froment
(1968). The latter authors have reported that the pyrolysis is
strongly inhibited. They introduced an inhibition function
multiplying the initial first-order rate coefficient of the pro-
pane disappearance. The variation of the rate coefficient with
conversion as obtained from an isothermal radical simulation
at 800 "C is shown in Figure 5 . The global first-order rate
coefficient varies over a factor of 5 between conversions
ranging from 30 to 65%. Consequently, the reaction scheme
presented here accounts for the inhibition, although a factor
of 5 is somewhat high. For the "data" shown in Figure 5 the
inhibition law, k = h o / l + ax,, proposed by Buekens and
Froment for the global first-order kinetics, yields ko = 7.5841
X lo4 and a = 2.005 X lo4. These unrealistically high values,
Ind. Eng. Chern. Fundarn., Vol. 17, No. 3, 1978 179
Figure 5. ~~kcoefficient activation energy for propane cracking
considered as a first-order reaction and derived from pseudo-iso-
thermal radical simulations.
which are nonsignificant at the 95% confidence level, probably
result from too strong a correlation between ko and a.
A much better fit is obtained by the relation
k=
+
1 bX, -
- 1 - 1.2318Xp
+
c dX, 1.9862 X +
7.7074 X 10-2X,
in which all the parameters are significant at the 95% proba-
bility level. The F-test also indicates that the latter expression
is superior to the former.
The model also accounts for the effect of the total pressure
and of the partial pressure of propane on the global rate
coefficient observed by Van Damme et al. (1975). The acti-
vation energy of the propane conversion taken as a first-order
process and obtained from pseudo-isothermal simulations at
775 and 800 OC was found to be a function of conversion,
represented in Figure 5 . The trend is in agreement with that
observed experimentally by Buekens and Froment, but the
values of the activation energy are somewhat high.
n-Butane Cracking
Low-temperature pyrolysis of n-butane has been modeled
by Blakemore and Corcoran (1969), Blakemore et al. (1973),
Powers and Corcoran (1974), and Allara and Edelson (1975).
Pacey and Purnell (1972~)have proposed a model for high-
temperature cracking.
In n-butane pyrolysis, ethane, ethylene, methane, propyl-
ene, hydrogen, and small quantities of 1-butene, acetylene,
and butadiene were found as products. The details of the re-
action scheme are shown in Table 11. Under normal pyrolytic
conditions two initiations, one leading to ethyl radicals and
one to methyl and 1-propyl radicals, are predominant.
Leathard and Purnell(l970) have shown that the l-C4H9*
radical mainly yields ethylene and an ethyl radical, while the
2-C4Hyradical mainly yields propylene and a methyl radical.
The isomerization of l-C4Hy proposed by Lin and Back
(1966b) is also considered. This is one of the major reactions
in n-butane pyrolysis.
Figure 6 shows the conversion and radical concentration
profiles along an isothermal reactor at 800 "C. It is clear that
none of the radicals ever attains a constant value. Also, the
concentration of radicals and molecules differs sometimes by
nine orders of magnitude. In Figure 7 a calculated product
distribution for the major species obtained from nonisother-
mal simulation is compared with experimental values.
Isobutane Cracking
Buekens and Froment (1971) have proposed a reaction
mechanism for isobutane cracking. Recently Bradley (1974)
180 Ind. Eng. Chem. Fundam., VoI. 17, No. 3, 1978

I
10

60

'0

20

- l 'S - b - 2 -15 -i L -0
-05 d 05 1 i 5 210g(V,/Fe)
-15
- -3 -25 1 .2 3 U 0 d s r 15 !~log~":Fol

Figure 6. Calculated concentration of radicals and molecules and Figure 8. Calculated concentration of radicals, molecules, and con-
conversion for isothermal cracking of n-butane: T = 800 O C ; Po = 2.0 version along an isothermal reactor for isobutane cracking: T = 775
atm abs; 6 = 0.44 kg of steadkg of butane. "C; Po = 1.4 atm abs; 6 = 0.4 kg of steam/kg of butane.

YIELD YIELD
wt %4 4"' %
I
15-1 I7

' x CIHS /

I
io io io 50 60 71

Figure 9. Product distribution vs. isobutane conversion: PO= 1.4 atm

Figure 7. Product distribution vs. n-butaneconversion:Po = 2.0 atm
abs; 6 = 0.4 kg of steadkg of butane; points, experimental; lines,
simulated.
also proposed a mechanism to explain the product distribution
obtained in shock tube pyrolysis. In the present work, hy-
drogen, methane, propylene, and isobutene were observed as
major products and small amounts of ethylene, allenes (pro-
padiene and methylacetylene), 2-butene, butadiene, and
higher aromatics were found (Froment et al., 1977). The
proposed mechanism, consisting of 86 reactions and involving
14 molecular species and 12 radicals, is shown in Table 11.
Reactions leading to the primary products have been dis-
cussed by Buekens and Froment (1971). Although small
amounts of both propadiene and methyl acetylene are ob-
served, the latter is the more stable compound. Hence, they
are considered as a single component, C3H4.It is reported that
methylacetylene is formed by the decomposition of the allyl
radical (Swarc, 1949; Amano and Uchiyama, 1963,1964)
C3H5- + C3H4 + He
Methylacetylene is not detected in propane cracking, however,
nor in n-butane cracking, in spite of the high concentration
of the allyl radical. It is only observed in isobutane cracking,
not even in propylene cracking. Therefore, methylacetylene
could be formed from isobutane and/or isobutene which are
not present as products in the cracking of the other species
considered. Schugerl and Happel (1972) have shown that in
isobutene cracking, methylacetylene is indeed a primary
product. Also, methylacetylene is only a secondary product
in isobutane cracking (Froment et al., 1977). I t may be con-
cluded that methylacetylene is formed from the methyl allyl
radical C4H7-obtained from isobutene by metathetical reac-
tions
abs; 6 = 0.4 kg of steamkg of butane; points, experimental; lines,
simulated.
C4H7- -+ C3H4 + CHy
This methyl allyl radical is an isomer of the unsaturated
radical C4Hy considered earlier. This mechanism also explains
the high selectivities for methane and the low selectivities for
isobutene at high isobutane conversions.
Formation of trans-2-butene is accounted for by the reac-
tion
i-C4H9' Z-C4Hs H- - +
The formation of 2-C4H8from 2-C4Hg-is not considered, since
the former is not found in n-butane or propane cracking. T o
explain the high selectivity for ethylene at high temperatures,
Bradley (1974) introduced the reactions which proceed via
"forbidden" routes
i-C4Hg- C2H4 C2Hb' -+ +
Instead, in the present study, metathetical reactions involving
vinyl radicals and unimolecular decomposition of C4H7-rad-
icals account for ethylene formation.
Calculated concentrations of the radicals, molecules, and
conversion, along an isothermal reactor operating at 775 "C
are shown in Figure 8. The product distribution obtained from
nonisothermal simulation is shown in Figure 9 as a function
of isobutane conversion. It can be seen that the agreement
between the experimental and calculated values is quite sat-
isfactory.
Olefins Cracking
In this section the cracking of ethylene and of propylene is
modeled on the basis of the extensive experimental results
recently reported by Froment et al. (1976b).
 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978 181

XI%) YIELD.wt % TI'CI YlELDIwt % I C ~ l

6oLl
log C, iradicals)

178

A;60 50 60
v C2H6

70 80 90
C2*6

100
I8O0

,780

I
loo
1500
0 IO 20 30 LO 50 60 70 80 90 100
% O F REACTOR LENGTH % O F REACTOR LENGTH

Figure 10. Calculated concentration profiles and product distribution Figure 11. Calculated concentration profiles and product distribution
along the reactor for ethylene cracking: PO = 1.5 atm abs; 6 = 0.4 kg along the reactor for propylene cracking: Po = 1.5 atm abs; 6 = 1.0 kg
of steamkg of ethylene; points, experimental; lines, simulated. of steamkg of propylene; points, experimental; lines, simulated.

Benson and Hougen (1967),Boyd et al. (1968), and Kunugi

et al. (1969) have proposed radical mechanisms for ethylene
cracking. According to Leathard and Purnell (1970), only
radical reactions would take place in paraffins pyrolysis, but
Danby et al. (1955) concluded that in the decomposition of
1-butene molecular reactions also occur. Silcocks (1955) has
reported that nitric oxide inhibits the ethylene cracking. Yet,
he does not exclude molecular reactions: methane would be
formed from 1-butene by such a mechanism while 1-butene
itself is formed by bimolecular collisions between ethylene and
ethane or between ethylene only.
The kinetic data on the addition of ethylene and butadiene
extrapolated from the low-temperature values of Bowley and
Steiner (1951) indicate that this reaction is as important as
any other propagation reaction. 0 10 20 30 LO 50 60 70 80 90 100
%OF REACTOR LENGTH
The high yields of the Cb+ fraction, even at low conversions,
indicate that many polymerization and condensation reactions Figure 12. Calculated concentration profiles and product distribution
along the reactor for the cracking of a mixture containing 42.2:18.4:
are taking place. The high molecular weight radicals are 39.4 wt % ethane-propane-n-butane:PO = 1.56 ata; 6 = 0.4 kg/kg of
mainly pradicals and these mainly decompose into high mixture; points, experimental; lines, simulated.
molecular weight olefins which further react by condensation.
For these reasons a few molecular reactions are included in
the scheme proposed here. propylene cracking have been discussed by Froment et al.
(1976b). A condensation such as
The major H-transfer reactions involve reactions of He and
CHa. yielding a vinyl radical. The addition reaction
CzH4 + H- C2H5.
C3H6 + C4H6 - polymer
-+
is also reported in the literature (Bowley and Steiner, 1951).
is also important. As a consequence, a t moderate conversions, No reliable kinetic data are available, however.
the methane selectivity is increased by The reaction scheme for propylene cracking is shown in
Table 11. Typical concentration profiles are shown in Figure
CzH4 + C2Hy --* C3H6 + CH3. 11.For an improvement of the fit, radicals heavier than C5Hlr
CzH4 + CH3. --* CzH3. + CH* and more molecular reactions would have to be considered.

In ethylene cracking a total of 66 reactions are considered Mixture Cracking

including three molecular reactions, as shown in Table 11.
Typical radical and molecular concentration profiles are
shown in Figure 10. It should be added that all high molecular
weight substances are lumped into a single species, C5+ and
that, since Cb+ decomposition was not considered due to a lack
of information, this introduces some error into the product
distribution.
Propylene cracking yields high amounts of acetylene in the
present work when compared with the work of Laidler and
Wojciechowski (1960) and Ingold and Stubbs (1951). The
acetylene formation is accounted for by the decomposition of
allyl radical, as discussed by Froment et al. (1976b) and con-
sidered previously in propane cracking
C3H5- - CzH2 + CHy
The condensation and decomposition zones of this radical in
Reaction schemes for the cracking of paraffinic mixtures
have been proposed by Murata et al. (1974) and Kubota et al.
(1969). The parameters obtained from single-component
cracking had to be adapted to get a satisfactory fit of the
mixture cracking, however.
In the present work the cracking of binary and ternary
mixtures containing ethane, propane, normal, and isobutane
experimentally studied by Froment et al. (1976a, 1977) was
simulated. The reaction scheme for mixture cracking was
obtained by superposition of the schemes for single-compo-
nent cracking. There was no need to adjust the parameters to
come to a satisfactory fit of the results. The interaction which
has been reported (Froment et al., 1977) in the cracking of
mixtures is directly accounted for by the detailed reaction
schemes set up for the cracking of single components. Calcu-
lated concentration profiles are shown in Figure 12 for an
182 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978
ethane-propane-n -butane mixture and are compared with
the experimental values.
In mixture cracking the ratios of concentrations of radicals
are altered, so that reactions which are not significant in sin-
gle-component cracking may become important in mixture
cracking. This is the case for the H-transfer reaction
C3H6 + H* -+ C3Hv + Hz
Allara has quoted two sets of values for the kinetic parameters
of this reaction ( A = 1.0 X l o l l , 5.0 X lolo; E = 3.8, 5.0).
Kunugi e t al. (1970) have used A = 2.5 X lo9 and E = 1.1.
Since this reaction is not very important in propane and n-
butane cracking because of the low concentration of H - radical,
any value can be used without much error. In mixtures
cracking, however, the Ha concentration is increased, due to
ethane decomposition. Only Kunugi's values gave satisfactory
results, whereas the other values predicted too much decom-
position of propylene. Isomerization of 1-C4Hg-to 2-C4Hg. is
also an important reaction in mixture cracking.
Conclusions
The proposed reaction mechanisms satisfactorily predict
the experimental results of single-component cracking for a
wide range of temperatures. The kinetic parameters were
obtained from the nonisothermal data under relaxation of the
pseudo-steady-state hypothesis used hitherto in kinetic
analysis and which has been shown to distort the values of the
kinetic parameters (Sundaram and Froment, to be published).
A unique set of kinetic parameters was used for each reaction
irrespective of the feed components. Since the parameters
were obtained from a simultaneous consideration of the
cracking of various single components, the reliability of the
parameters is thought t o be greatly improved as compared
with previous attempts. The superposition of the reaction
schemes for single-component cracking does account for the
interaction observed in mixture cracking. The complete re-
action scheme presented here now allows an accurate simu-
lation of industrial gas cracking.
Acknowledgment
The support of the Process Data Group of K.T.I., Zoeter-
meer, the Netherlands, is gratefully acknowledged.
Nomenclature
A = frequency factor, s-l or L mol-l s-l
E = activation energy, kcal/mol
Fj = molar flow rate of j t h component, mol/s
Fo = inlet molar flow rate of hydrocarbon, mol/s
h = reaction rate coefficient, s-l
N = number of reactions
n = reactionorder
P = pressure, atm abs
P o = outlet pressure, atm abs
R = gas constant, kcal/mol K
Rj = rate of formation of j t h component per unit volume of
reactor, mol L-l s-l
ri = reaction rate of i t h reaction, mol L-l s-l
sij = stoichiometric coefficient of j t h component in i t h re-
action
T = temperature, "C or K
T o = outlet temperature, "C or K
V = reactor volume, L
V , = equivalent reactor volume, L
x = conversion of key component
X B = n-butane conversion, %
X ~ B = isobutane conversion, %
X , = propane conversion, %
2 = reactor length coordinate, m
6 = dilution factor, kg of steam/kg of hydrocarbon
D = area of cross section of the reactor including conversion
factor from m3 to L
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Received for reuiew February 22,1977
Accepted April 20,1978