MODELING

OF THERMAL

THERMAL

CRACKING

CRACKING
OF ETHANE,
AND THEIR MIXTURES

KINETICS-I
PROPANE

KM
SUNDARAM and G F FROMENT
Laboratorlum voor Petrochemlsche Technlek, Rllksumversltelt, Gent, Belgium
(Received 1 July 1976, accepted

18 August 1976)

Abstract-Molecular reaction schemes

for the thermal cracking of ethane, propane and then matures have been
derived from observed
product dlstnbutlon,
radical mechanisms,
and thermodynamic
prmciples
The rate
parameters were determmed m a systematic way by estimatmn techmques mmimztng a multi-response ObJectWe
fun&Ion Dlscrunmatlon between rival models was based upon physical cntena and statM~ca1 tests The reaction
scheme obtamed by the superposlhon of smgle component crackmg also safisfactonly fits the data for the crackmg
of mixtures of ethane and-propane
INTRODUCTION

Hydrocarbon pyrolysis IS the major source of ethylene,

propylene, butadlene and aromatics, the pnmcpal feedstocks of the petrochemical Industry For the design of
the crackmg cod an overall kmetlc equation for the feed
disappearance 1s generally not sufficient, since the predlctlon of the product drstnbutlon 1s a very nnportant
design aspect This then requires a set of kmetic equations for a set of reactions ylelchng the products of
interest Although the reactions proceed via free radical
mechamsms[l],
for slmulatlon or design purposes sunphfied so-called molecular schemes are adopted to cmcumvent the mathematical dlaculties encountered with
the integration of the system of stti ddferential equations associated with radical reactions Several molecular
reaction schemes have been published for the crackmg
of ethane and propane[2,4-fj]
They lead to sets of
dlfferentlal equations contammg
a large number of
kmetlc parameters and these have been obtained so far
by a tnal and error procedure, untd the results of the
mtegrafion match the experimental results Such a trial
and error procedure for the estimation of the parameters
1s not qmte satisfactory
In other areas of applied
kmetlcs, e g m heterogeneous
catalysis the kmetlc
parameters are obtamed m a much more systematic and
rigorous way, e g by least square estimation Further,
statistical tests are apphed to mvestlgate the validity of
the model and of the associated parameters The present
paper applies such a systematic approach to the kinetic
modeling of the crackmg of hydrocarbons
molecular
reaction schemes are postulated, accounting as much as
possible for the true radical mechamsm,
the model
parameters are estimated by regression and the relevant
statistical tests are applied A scheme leading to slgmficantly negative parameters or to abnormal values for
the activation energy of one or several of the reactlons 1s
rejected If more than one model is left m competition
after these crlterla have been applied, the fit of the
models IS compared to permit selection of the final
model The strategy outlined above IS completely analo601

gous to that used m the kmetlc modelmg of heterogeneously catalyzed reactions accordmg to Hougen and
Watson and recently discussed by Froment[7]
EXXANECRACKING
Expenmental
data
The experimental data used m tlus modeling work are
those published by Froment et al [3] These data were
obtamed m a pilot reactor for outlet total pressures of 1 5
and 2 atm abs and dtlution factors of 0 4 and 10 kg
steam/kg hydrocarbon
The outlet temperatures ranged
from 780 to 85OC, the reference temperatures used m
the calculation of the equivalent reactor volumes from
775 to 825C The Reynolds number varied from 5000 to
10,000, the pressure drop from 0 3 to 0 5 atm
Reactton schemes
The basis for the development of the reaction schemes
are the product dlstibubons
In ethane crackmg the mam
products are ethylene, hydrogen and methane Small
quantities of propane, propylene,
acetylene and butadlene are also found Imtlatlon, propagation by radicals
and termmatlon steps are involved 111the process The
radical reactions are used here as a guide for buddmg the
molecular model The maJor pathway to ethylene may be
written
C,Hs + H A
C,H; *I_

C,H: + H,

(1)

C,H, + H

(2)

Addition of these two radical reactions

cular equivalent
C2H6 The correspondmg

C2H4 + Ht

kmetlc equations
9

yields the mole-

(3)

may be wntten

= k; (C,H&H)

(4)

602

SUNDARAMand G

F FROMENT

2CZH.5-

It IS well known from propane

the reaction

When pseudo steady state 1s attamed

k;GHdW)
Ehmmatlon

= W3-I;)

C,H, -

(6)

of (CzH3 between (5) and (6) leads to

w =

L;(C,HJ(H)

(7)

C,H:

CzH4--+

b,H, + b,CH, + b&H,

are chosen to satisfy the mass

whereby
b,, 6,
balances for carbon and hydrogen
This approach 1s
hmlted to a narrow range of operating conditions,
however, and it was preferred to reflect the true nature
of the reactions more closely The following reactions
have
been
proposed
to
account
for
acetylene
production [2, i]
C,H, -

CzH, + H,

C,H, -

&Hz + CH,

(9)
(10)

It follows from thermodynamic

calculations based on
Rossmls tables for free energies of formation[9] that (9)
1s not feasible under the usual pyrolytic condltlons, so
that only (10) was retained
To account
for propylene
formation
Pacey
and
Purnell[lO] proposed the followmg radical reaction at
temperatures above 640C
C,H; + C,H, The molecular

C,H, + CH;

equrvalent was wrltten

C,Hs + CzH4 -

C,Ha + CH,

Propylene may result from the decomposition

accordmg to, m molecular terms
C,Hs The formatlon

(1 >

(12)
of propane

CsH6 + Hz

of propane IS accounted

crackmg,

however,

CzH4 + CH.,

that

(15)

CzH4 + 2CH.,

(16)

Finally, the butadlene formation was ascribed to the

decomposltlon of the C,H; radical The latter ongmates
from
C,H, + C,H: -

(8)

and this leads to adding a reverse step to the molecular

reaction (3) From thermodynamics It follows that such a
reactmn 1s indeed reversible under normal crackmg
condltlons Reaction (3) accounts for more than 90% of
the total reaction rate and 1s therefore common to all the
models developed These dtier by one or more of the
secondary reactions For these secondary reactlons gross
molecular models have been used hke, e g [5,6,8]

(14)

1s equally important
The followmg reactlon was also mcluded m one of the
models to account for methane formation
2C2H,5 -

These equations show that the rate of formation of HZ

and C2H4 obeys first order with respect to C2Hs, which IS
m agreement with the experimental observations
The followmg radical reaction also takes place
&Ha + H -

C,Hs + CH,

and therefore

C,H;

the butadlene formation

C,H, + C,H, -

(17)
1s wrrtten as

CdH6

(18)

Three models were set up on the basis of the above

considerations
They are aven m Table 1 Models II and
III dfier from I m that they dont include propane
decomposltlon reactions
Model drscnmmaflon
and parameter eshmatron
The kmetlc equations for the reactions are given m
Table 1 All the reactions, except (2) (Table 1) were
considered to be elementary,
so that the order corresponds to the molecularrty Reaction (2) LS more complex and first order was assumed for it
To determine the model parameters the kinetic equations of model I, II and III have to be substituted mto the
appropriate contmmty equations for the components,
and these have to be mtegrated and compared with the
Integral reactor data It should be mentioned here that
the experimental data were reduced to lsothermahty by
means of the equivalent reactor volume concept, dlscussed and applied by Van Damme et al [2] and by
Froment et al [3] The contmmty equations for the components can be written
-f$=-R,=-zs,,r,

(19)

where S, represents the stolchlometnc coefficient for the

Ith component m the lth reaction
The parameters were estimated by non linear regression by means of Marquardts algorithm The multlresponse nature of the problem was accounted for by
mmlmlzmg the weighted sum of squares of residuals on
the molar flow rates F, of the reaction components at the
exit of the reactor

(13)
for by

where w, 1s the weighting factor

The second summation

Modehng of thermal crackmg

Model I

(2) Z&H, A

CJ-I, + H,

C,H. + CH,

(3) C,H. *

C,H, + H,

(4) C,H. 3

C,H, + CH,

(5) C&J6&GH,+C&
(6) C,H, + CZH, A

C,H,
Model II

(1) CZH, &C&_,+Hz

(2) ZCZH,*

C,H, + CH,

(5) C&L &C2Hz+CH,

(6) C,H, + C,H, A
(7) 2&H,

C&

C,H, + 2CJ-L

(8) C,H, + C,H, -%

C,Hs + CH.

Model III
(1) C,&
(2) 2&H,

*I

GIL

603

IS carried out over the n experiments

The Integration
of
the set of dlfferentlal equations was performed by means
of the Runge-Kutta-GB
routme
Model I was reJected, since several parameters were
found to be negative Model II was reJected, m spite of
positive values for the parameters, because ks (Table 1)
was found to be mdependent of temperature and because
kl (Table 1) was not slgmficant at the 95% confidence
level With model III all the parameters were positive,
slgndicant at the 95% confidence level and temperature
dependent As shown m Fig 1 no bias could be detected
m the calculated vs experimental fiuxes for ethane,
ethylene, hydrogen and methane Estunated parameters
for Model II and III at 800 and 825C are shown m Table
2 The bmary correlation
coefficients
between
the
parameter estimates were found to be very small The
temperature dependence of the rate coefficients 1s shown
m the Arrhemus plot of Fig 2 The parameters were not
estimated at 85OC, smce only five expenments were
available at that temperature Also, at 775C the yields of
acetylene, butadiene and propane were extremely low
Therefore, the weights of these responses were set zero
at that temperature and only k, and k, were estnnated
The activation energies and frequency factors are gven
m Table 3 A value of 65 20 kcallmole IS obtamed for the
main reactlon (1) m Table 1 From a study of the overall
kmetics Froment et al [3] derived values rangmg from
59 30 to 6194 k&/mole
depending upon the experlmental condltlons It should be added that Model II, Model
III and even Model I lead to an almost identical value of
65 00 kcal/mole, which IS not surpnsmg, smce the mam
reaction accounts for roughly 90% of the total ethane
conversion
Finally, it should be added that more accurate rate parameters for some of the minor secondary
reactions could be obtained from processes m which
they are more important This will be the case, e g for
the parameters of reaction (3) (Table l), wbch 1s far
more important m propane crackmg
In this way It
becomes possible to develop a coherent and precise set
of kmetrc data which can be used for the crackmg of
mixtures of hydrocarbons This will be illustrated m what
follows

Table 1 Models for ethane crackmg

(1) CJ-L &

kmetlcs-I

+ I-L

- *2 C,H, + CJL

PROPANECRACKING
Expenmental
data
The data used m this work were obtamed by Van
Damme et al [2] m the followmg range of operatmg
varrables Propane flow rate from 2 to 5kg/hr, steam
dilution 0 3-l 0 kg/kg propane, outlet temperature 70087OC, outlet pressure 1 2-2 3 atm abs , pressure drop
0 3-O 5 atm
Notation used in Table 1

Kc,
Kc<

775

800

825C

8 895 x IO-
9 847 x lo-

1 276 x lo-
1 375 x 10-Z

1 800 x lo-
1 890 x lo-

F, = sum of flow rates of reactants,

products and steam

= 2 F. + steam
r-1
K,,,

Kc, = equhbrmm

constants based on concentration

604

Erperlmental

2,s

Fig

1 Expenmental

vs calculated

Table 2 Estimated

Rate
coefficient

Table

3 Arrhemus

Rate coefbent

parameters

4 652
3 850
9 814
1 026
7 083

FROMENT

CHL

75

fluxes at the extt of the reactor for ethane crackmg

parameters

for ethane crackmg for models

t value

II and III

Temp = 825C
parameter value
(set?
or tl mole-set-)

1 value

4 9350
3 6044 x 1o-3
43 1333
6 5244 x 1Ot
3 7839 x lo-
71 OOOO

48 3
021
53
42
109
91

2 4160
1 9893 x 10-Z
29 8083
4 0638 x 103t
30 7083t

Model III
80 5
93
82
36
192

4 937s
3 9919 x 10-2
44 2055
6 3128 x 10t
715306t

513
12 2
62
43
21 0

crackmg

Model III

E (kcal/mole)
65
65
36
41
60

20
25
92
26
43

reviewed recently by Buekens and Froment [ 1 l] and Allara and Edelson[ 121 The molecular reaction schemes
presented here were constructed on these bases They
consist of 9 reactions, contams 10 species and are shown
m Table 4 Only the malor reactions not encountered yet
m the section on ethane crackmg wdl be discussed here
The followmg radical reactions account for the formation of propylene and hydrogen
C,H, + H -

Reactron

Model III

Model II
77 8
37
69
36
77
115

for ethane

x lOI
x 10
X lo*
x lO*t
x 1Ot

2 4054
0 0171
21 9302
6 4322 x 103t
9 7872 x 10m3
27 9250

A (see- or tl mole- set-)

k,
kz
%
%
k,

Imol/Ohr)

Temp = 800C
parameter value
(set- or tl mole- set-)

k,
k+
k,
k,
k,
ks

and G

SUNDARAM

C,H; + H,

(20)

C3H6 + H

(21)

scheme

Several molecular
models
have
been
proposed
for
propane crackmg, most recently by Van Damme et al [2]
and Murato and Salto[6]
The parameters were determmed by a trial and error procedure
Detaded radical
mechamsms for this reaction have been dlscussed and

&HI; -

By adding up these two radical reactions the

hydrogenation
already mentioned m the section
ethane as eqn (13) 1s obtamed

deon

Modehng of thermal crackmg kmetlcs--I

kfhr-lor(llt/mol

k(Lath

hrl

---.

C,H, -

II hr)

CzH, + CH,

(24)

CRACKlNG

PROPPlNE
ETHANE

605

Ethane formatlon
reactlons

CR*CK,NG

1s accounted

C,H, + C,H: -

106

by the followmg

C,H; + CzH6

C,H, + H Addltlon
reactlon

for

C,H;

(25)
(26)

of (25), (26) and (21) leads to the molecular

C,H, + C&H, -

CxH6 + CzHs

(27)

Secondary reactlons leadrng to acetylene and hutadlene

were dlscussed under ethane crackmg already
The monotomc mcrease of the ethylene and methane
selectlvlty and the dechne of the propylene selectivity 1s
accounted for by
2GHa -

3&H,

(28)

2C3H6 -

3cH.# + l/2&

(29)

and
04
(lIK)

Fig 2 Arrheruus plot for ethane cracking (Model III) and propane cracking (Model I)
Table 4 Reachon schemes for propane crackmg
Model I
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)

C,H, -

C,H, + CH,

C,H. =
C,H, + Hz
C,H. + CzH. C&L + WI.
2C,H, 3&H.
2C3H, 0 Xa + 3CH,
CzH, + CH,
C 3H 6-&Ha + C,H,-, GH. + CH,
C,H, z=+ GH. + Hz
C,H, + &Hz C&.
Model II

(1)
(2)
(4)
(6)
(7)
(8)
(9)
(10)

C,Hs CzH, +
C,H. e
C,Hs +
2C,H, 3GH.,
C,H, =
C&I, +
c,& + GIL C,H, =
CzH. +
C,H. + &Hz -

2C,H, (I I) 2C,Hs -

Kc, values

CH,
Hz
CH,
C,H, + CH,
Hz
Cd%

CJL. f CJLo
C,H, f (XL. + CH.

77SC, 0 074, 8OOT, 0 102, 825C. 0 138

The following reactions

ethylene and methane

account

for the formatlon

of

C3Hs + CH; -

CJH; + CH,

(22)

C,H; -

C2H4 + CH;

(23)

Addition of the two reactions ytelds

In (29) Cs really represents the C, fraction although in

propane crackmg this mamly consists of benzene The
amount of hydrogen m the C,-compound IS neglected In
propane cracking the C5+-weight yield varies between 3
and 6%, depending upon the total pressure and the steam
tiufion
The followmg reactions were mtroduced mto
Model II, shown m Table 4 Instead of reactions (3) and
(5) of Model I, also shown m Table 4
2C,Hs -

CzH6 + C,I&o

2C,H, -

C,Hs + &He + CH,

Model drscnmrnatron
and parameter estmatrott
Because of the large number of parameters to be
es&mated the computation time increased drastically
Precise estunatlon of the parameters of the secondary
reactlons was difficult Both Models I and II contain
reactions hke (8) and (9) which are more unportant m
ethane crackmg and for which the parameters had already been determined accurately It 1s then preferable
to take over these parameter values In add&on, k6 and
k, related to minor reactions mvolvmg acetylene and
butene were estunated by tnal and error The parameter
estunates obtamed by Marquardts algorithm at 800C are
shown by way of example m Table 5
Model II led to slgmiicantly negative values for the
rate coefficient of reaction (11) (Table 4), at all temperatures and was rejected for this reason
All the
parameters of Model I were posltlve and the activation
energes were plausible It should be mentioned, though,
that k3 1s less accurately determmed than the other
parameters This IS not surprlsmg smce the ethane selectivity does not exceed 3 2% Further, ethane was also
present m the feed as an Impurity, and this decreased
somewhat the accuracy of Its determination Dficulfies

606
Table 5

Rate
coefficient

SUNDARAMand G

Estimated parameters

t value

23409
2 126.5
23 6350t
0 7208
0 8164

80 3
79 4
18
160
22 1

were encountered
in estlmatmg
kJ at 85OC, so that its
value at that temperature
was extrapolated
from the
values at 775, 800 and 825C
All the estnnated parameters
of Model I were highly
sign&ant
at the 95% confidence level
The bias was tested by plottmg the calculated
and
experlmental molar flow rates at the exit of the reactor as
shown m Fig 3 for 825C, e g The rate parameters all
obey the Arrhemus relation The frequency factors and
the activation energies for Model I are hsted m Table 6
and shown m Fig 2 Since the first two reactlons of
Table 6

Arrhemus parameters

Rate wefficlent
k,
kz
?
k:
k,
k,
k,
kg

for propane crackmg

A (set- or tl mole- see-)

4692x
5 888 x
2 536 x
1 514 x
1423 x
3 794x
5 553 x
4 652 x
1 026 x

1O1O
100
lO*V
10
109
10
lo.?
lOI3
10t

Model I

E (kcal/mole)
50
51
59
55
45
59
60
65
41

60
29
06
80
50
39
01
20
26

FROMENT

for propane crackmg

Model I
parameter value
(set- or tl mole- see-)

kl
k,
k,
k,
k,
k 0
k II

Model II
parameter value
(se&
or tl mole-set-)

t value

2 8549
18572
0 2674
6 7880 x lo-*
- 8 5283 x lo-*

610
73 7
57
28
-20

Model I account for more than 90% of the total propane

consumption
the overall rate of disappearance
of propane was based upon these two reactrons The activation
energy was found to be 50 93 kcal/mole, a value which
has to be compared
with 52 4 kcallmole
obtamed
by
Buekens and Froment [ 1 l] at zero converslon and 49 6 to
51 2 kcal/mole
(dependmg
upon the total pressure and
steam ddutlon) obtamed by Van Damme et al [2]
E-PROPANE

Fig 3 ExperImental

,molIh:!

MIXTUWS

Recently, Murata et al [13] set up a radical reaction

scheme
to explain
the experlmental
results
of the
pyrolysis
of
par&n
hydrocarbon
mixtures
The
parameters were determmed by trial and error
In this work a molecular reaction scheme, shown m
Table 7, was constructed,
contammg all the major reactlons of ethane and propane crackmg The parameters of
the reactions
were sunply taken over from the pure
component
crackmg, dependmg upon the Importance of
the reactlon m either ethane or propane crackmg
The
source of each parameter value 1s also given m Table 7
Only the frequency
factor of a minor reaction, namely
butene formatlon had to be shghtly adapted, since it was

30
Ex~rerrmcnta,

at 800C

40

20

3 H6 f-JH6

vs calculated fluxes at the exit of the reactor

for propane crackmg

Model I

Modelmg
Table

7 Reaction

of thermal

scheme

1
2
3
4
5
6
7
8
9
10

llsecor

E, ethane,

P *, frequency

factor

less sigmficantly determmed from the smgle component

crackmg The model was checked agamst experimental
data obtamed with feeds contammg 25, 50 and 75 wt%
ethane at several steam ddutlons and total pressures and
reported m detad by Froment et al [3] The slmulatlons
accounted for the experlmental temperature and pressure
profiles Some results of the slmulatlons are compared
with the experlmental data m Fig 4 The agreement 1s
excellent, mdlcatmg that the model resultmg from the
superposition
of the models for ethane and propane
crackmg does account for the interaction reported by
Froment et al [3] This IS probably due to the close
connection
of these molecular models with the true
radical schemes of the reactions

CONCLUSIONS

In tlus work a rather rigorous approach has been

adopted for model buddmg m thermal crackmg reactions
Molecular
reaction schemes were set up, based as
closely as possible on radical schemes The dlscnmmatlon between rival models was based upon physlcochemical constramts for the parameters and the goodness of fit of the model The parameters were obtained
by estnnabon,
usmg a multlresponse
approach and
mmlmlzmg a we&ted
sum of squares of residuals by
means of Marquardts non linear regression routme

x
x
x
x
x
x

607

murture crackmg
E (kcal/mole)

t&

4 692
5 888
2 536
1 514
1 423
3 794
10 x
4 652
1 026
7 083

C,H. C,H, + CH,

C 3H 8--C,Ha+H~
C3Hs + CJ-L C,Hs + CSHG
CaHd 3&H,
ZC,Hs 0 5C, + 3CH.
C,H, +
CzH, + CH.
C,H, + C,H, Cd& + CI-L
C,H, =
CzH, + Hz
C,Hd + C,Hz C.H,
C,H, -I-C,H, C,H, + CH,
P, propane,

kmetlcs-I

for ethane-propane
A

Reachon

crackmg

10
10
10t
10
lo9
10

10-t
x lOI
x 109
x 10V

modtied

Source
P

50 60
51 29
5906
55 80
45 50
59 39
60 01
65 20
41 26
60 43
w&h respect

P
P
P

P
P

P*
E
E

to propane

This puts model bulldmg m thermal crackmg reactions

on the same ngorous basis as that m reactions catalyzed
by sohds

Acknowledgemenf-The
support of the Process
K T I , The Hague, The Netherlands,
IS gratefully

Data Group of
acknowledged

NOTATION

frequency factor, set-, or 1 mole- set-

coefficients m gross molecular reaction
actlvatlon energy, kcal/mole
molar flow rate of Jth component, moles/hr
estimated molar flow rate of Jth component,
moles/hr
total molar flow rate, mole&r
concentration
units
eqmhbrmm
constant
m
(moles/l )*,
set- ,
for
ith
reaction,
rate
coefficient
1 mole- set- or hr-, 1 mole- hr-
change m moles, moles
total pressure, atm
reaction rate for rth reaction
gas constant, kcal/mol K or atm 1 mole- K-
stolchlometrlc
coefficient of component 1 m &h
reaction
temperature, K

Fig

Product

dlstrlbutlon
vs propane conversion
Cracking of a 50/50 wt% mixture of ethane
Dllutlon factor 0 4 kg steam/kg mixture Lines, expernnental,
Pomts, calculated

and propane

K M SUNDAUM and G F FROMENT

608
t
v,
x,
W,

t values
equivalent reactor volume, 1
propane conversion
wetghttug factor for Jth component

REFEXFNCES
[l] Laldler K J , Chemical Kmetxs, 2nd Edn McGraw-Hdl,
New York 1%5
[2] Van Damme P S , Narayanan S and Froment G F ,
AZChEJ
1975 21 1065
[3] Froment G F , Van de Steene B 0, Van Damme P ,
Narayanan S and Goossens A G , Znd Eng Chem Proc
Des Devpt 1976 15 495
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