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Laboratorlum voor Petrochemlsche Technlek, Rllksumversltelt, Gent, Belgium
(Received 1 J uly 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 ma systematic way by estimatmn techmques mmimztng a multi-response ObJ ectWe
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
Hydrocarbon pyrolysis IS the major source of ethylene,
propylene, butadlene and aromatics, the pnmcpal feed-
stocks 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 pre-
dlctlon of the product drstnbutlon 1s a very nnportant
design aspect This then requires a set of kmetic equa-
tions for a set of reactions ylelchng the products of
interest Although the reactions proceed via free radical
mechamsms[l], for slmulatlon or design purposes sun-
phfied so-called molecular schemes are adopted to cm-
cumvent the mathematical dlaculties encountered with
the integration of the system of stti ddferential equa-
tions 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 slg-
mficantly 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 analo-
gous to that used m the kmetlc modelmg of hetero-
geneously catalyzed reactions accordmg to Hougen and
Watson and recently discussed by Froment[7]
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 bu-
tadlene are also found Imtlatlon, propagation by radicals
and termmatlon steps are involved 111 the process The
radical reactions are used here as a guide for buddmg the
molecular model The maJor pathway to ethylene may be
C,Hs + H A C,H: + H,
C,H; *I_ C,H, + H
Addition of these two radical reactions yields the mole-
cular equivalent
C2H6 - C2H4 + Ht (3)
The correspondmg kmetlc equations may be wntten
9 = k; (C,H&H) (4)
When pseudo steady state 1s attamed
k;GHdW) = W3-I;) (6)
Ehmmatlon of (CzH3 between (5) and (6) leads to
w = L;(C,HJ(H)
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,H:
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]
CzH4--+ b,H, + b,CH, + b&H,
whereby b,, 6, are chosen to satisfy the mass
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]
It follows from
C,H, - CzH, + H,
C,H, - &Hz + CH,
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, - C,H, + CH;
(1 >
The molecular equrvalent was wrltten
C,Hs + CzH4 - C,Ha + CH,
Propylene may result from the decomposition of propane
accordmg to, m molecular terms
C,Hs - CsH6 + Hz
The formatlon of propane IS accounted for by
2CZH.5 - C,Hs + CH,
It IS well known from propane crackmg, however, that
the reaction
C,H, - CzH4 + CH.,
1s equally important
The followmg reactlon was also mcluded m one of the
models to account for methane formation
2C2H,5 - CzH4 + 2CH.,
Finally, the butadlene formation was ascribed to the
decomposltlon of the C,H; radical The latter ongmates
C,H, + C,H: - C,H;
and therefore the butadlene formation 1s wrrtten as
C,H, + C,H, - CdH6
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 cor-
responds to the molecularrty Reaction (2) LS more com-
plex and first order was assumed for it
To determine the model parameters the kinetic equa-
tions 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, dls-
cussed and applied by Van Damme et al [2] and by
Froment et al [3] The contmmty equations for the com-
ponents can be written
where S, represents the stolchlometnc coefficient for the
Ith component m the lth reaction
The parameters were estimated by non linear regres-
sion by means of Marquardts algorithm The multl-
response 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
where w, 1s the weighting factor The second summation
Modehng of thermal crackmg kmetlcs-I 603
Table 1 Models for ethane crackmg
Model I
& CJ -I , +H,
Z&H, A C,H. + CH,
C,H. * C,H, + H,
C,H. 3 C,H, + CH,
C,H, + CZH, A C,H,
Model II
ZCZH, * C,H, + CH,
C,H, + C,H, A C&
2&H, a C,H, + 2CJ-L
C,H, + C,H, -% C,Hs + CH.
Model III
C,& *I GIL + I-L
2&H, - C,H, + CJL
775 800 825C
Kc, 8 895 x IO- 1 276 x lo- 1 800 x lo-
Kc< 9 847 x lo- 1 375 x 10-Z 1 890 x lo-
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 experlmen-
tal 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 ac-
curate 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
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 700-
87OC, outlet pressure 1 2-2 3 atm abs , pressure drop
0 3-O 5 atm
Notation used in Table 1
F, = sum of flow rates of reactants, products and steam
= 2 F. +steam
K,,, Kc, = equhbrmm constants based on concentration
Er per l ment al Imol/Ohr) CHL
2,s 75
Fig 1 Expenmental vs calculated fluxes at the extt of the reactor for ethane crackmg Model III
Table 2 Estimated parameters for ethane crackmg for models II and III
Temp = 800C Temp = 825C
Rate parameter value parameter value
coefficient (set- or tl mole- set-) t value (set? or tl mole-set-) 1 value
Model II
k, 2 4054 77 8 4 9350 48 3
k+ 0 0171 37 3 6044 x 1o-3 021
k, 21 9302 69 43 1333 53
k, 6 4322 x 103t 36 6 5244 x 1Ot 42
k, 9 7872 x 10m3 77 3 7839 x lo- 109
ks 27 9250 115 71 OOOO 91
Model III
2 4160 80 5 4 937s 513
1 9893 x 10-Z 93 3 9919 x 10-2 12 2
29 8083 82 44 2055 62
4 0638 x 103t 36 6 3128 x 10t 43
30 7083t 192 715306t 21 0
Table 3 Arrhemus parameters for ethane crackmg Model III
Rate coefbent A (see- or tl mole- set-) E (kcal/mole)
k, 4 652 x lOI 65 20
kz 3 850 x 10 65 25
% 9 814 X lo* 36 92
% 1 026 x lO*t 41 26
k, 7 083 x 1Ot 60 43
Reactron 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 deter-
mmed by a trial and error procedure Detaded radical
mechamsms for this reaction have been dlscussed and
reviewed recently by Buekens and Froment [ 1 l] and Al-
lara 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 for-
mation of propylene and hydrogen
C,H, + H - C,H; + H,
&HI; - C3H6 + H
By adding up these two radical reactions the de-
hydrogenation already mentioned m the section on
ethane as eqn (13) 1s obtamed
Modehng of thermal crackmg kmetlcs--I 605
kfhr-lor(llt/mol hr l k(Lath
II hr)
C,H, - CzH, + CH,
Ethane formatlon 1s accounted for by the followmg
C,H, + C,H: - C,H; + CzH6
C,H, + H - C,H;
Addltlon of (25), (26) and (21) leads to the molecular
C,H, + C&H, - CxH6 + CzHs
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&
(lIK) 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
Fig 2 Arrheruus plot for ethane cracking (Model III) and pro-
pane cracking (Model I)
Table 4 Reachon schemes for propane crackmg
Model I
(1) C,H, - C,H, + CH,
(2) C,H. = C,H, + Hz
(3) C,H. + CzH. - C&L + WI.
(4) 2C,H, - 3&H.
(5) 2C3H, - 0 Xa + 3CH,
(6) C H 3 6-
- CzH, + CH,
(7) &Ha + C,H,-, GH. + CH,
(8) C,H, z=+ GH. + Hz
(9) C,H, + &Hz - C&.
Model II
(1) C,Hs - CzH, + CH,
(2) C,H. e C,Hs + Hz
(4) 2C,H, - 3GH.,
(6) C,H, = C&I, + CH,
(7) c,& + GIL - C,H, + CH,
(8) C,H, = CzH. + Hz
(9) C,H. + &Hz - Cd%
(10) 2C,H, - CJL. f CJLo
(I I) 2C,Hs - C,H, f (XL. + CH.
Kc, values 77SC, 0 074, 8OOT, 0 102, 825C. 0 138
The following reactions account for the formatlon of
ethylene and methane
C3Hs + CH; - CJH; + CH,
C,H; - C2H4 + CH;
Addition of the two reactions ytelds
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 al-
ready 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 tem-
peratures 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 selec-
tivity 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
Table 5 Estimated parameters for propane crackmg at 800C
Model I Model II
Rate parameter value parameter value
coefficient (set- or tl mole- see-) t value (se& or tl mole-set-) t value
kl 23409 80 3 2 8549 610
k, 2 126.5 79 4 18572 73 7
k, 23 6350t 18 - -
k, 0 7208 160 0 2674 57
k, 0 8164 22 1 - -
k 0 6 7880 x lo-* 28
k I I - - - 8 5283 x lo-* -20
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 for propane crackmg Model I
Rate wefficlent A (set- or tl mole- see-) E (kcal/mole)
4692x 1O1O 50 60
5 888 x 100 51 29
2 536 x lO*V 59 06
1 514 x 10 55 80
1423 x 109 45 50
3 794x 10 59 39
5 553 x lo.? 60 01
4 652 x lOI3 65 20
1 026 x 10t 41 26
Model I account for more than 90% of the total propane
consumption the overall rate of disappearance of pro-
pane 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]
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 reac-
tlons 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
Ex~rerrmcnta, ,molIh:!
30 40
3 H6 f-J H6
Fig 3 ExperImental vs calculated fluxes at the exit of the reactor for propane crackmg Model I
Modelmg of thermal crackmg kmetlcs-I
Table 7 Reaction scheme for ethane-propane murture crackmg
Reachon A llsecor t& E (kcal/mole) Source
1 C,H. - C,H, + CH,
2 C H -C,Ha+H~
3 8-
3 C3Hs + CJ-L - C,Hs + CSHG
4 CaHd - 3&H,
5 ZC,Hs - 0 5C, + 3CH.
6 C,H, + CzH, + CH.
7 C,H, + C,H, - Cd& + CI-L
8 C,H, = CzH, + Hz
9 C,Hd + C,Hz - C.H,
10 C,H, -I- C,H, - C,H, + CH,
4 692 x 10
5 888 x 10
2 536 x 10t
1 514 x 10
1 423 x lo9
3 794 x 10
1 0 x 10-t
4 652 x lOI
1 026 x 109
7 083 x 10V
50 60 P
51 29 P
5906 P
55 80 P
45 50 P
59 39 P
60 01 P*
65 20 E
41 26 E
60 43 E
P, propane, E, ethane, P *, frequency factor modtied w&h respect to propane
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
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 dlscnmma-
tlon between rival models was based upon physlco-
chemical constramts for the parameters and the good-
ness 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
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 Data Group of
K T I , The Hague, The Netherlands, IS gratefully acknowledged
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,
total molar flow rate, mole&r
eqmhbrmm constant m concentration units
(moles/l )*,
rate coefficient for ith reaction, set- ,
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
temperature, K
Fig 4 Product dlstrlbutlon vs propane conversion Cracking of a 50/50 wt% mixture of ethane and propane
Dllutlon factor 0 4 kg steam/kg mixture Lines, expernnental, Pomts, calculated
t values
equivalent reactor volume, 1
propane conversion
wetghttug factor for Jth component
[5] Petryschuk W F and Johnson A I, Can J Chem Engng
1%2 46 172
[6] Mnrata M and Smto S , J Chem Engng Jopan 1975 8 39
[7] Froment G F , A ZCh E I 1975 21 1041
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[9] Rossrm et al, Selected Values of Thennodynamrc Properties
of Hydrocarbons and Related Compounds Carneme Press
[l] Laldler K J , Chemical Kmetxs, 2nd Edn McGraw-Hdl, [lo] Pacey P D and Purnell J H , Znd Engng Chem Fund1 1972
New York 1%5 11 233
[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 ,
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[l l] Buekens A G and Froment G F , Znd Engng Chem Proc
Des Devpt 1968 7, 435
[12] Allara D L and Edelson D , Int J Chem Kmefxs 1975 7
[4] Shah M I, Znd Engng Chem 1967 59, 71
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