Organic Geochemistry 42 (2011) 439450

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Thermal evolution of n- and iso-alkanes in oils. Part 1: Pyrolysis model for a

mixture of 78 alkanes (C1C32) including 13,206 free radical reactions
V. Burkl-Vitzthum a,, R. Bounaceur a, P.-M. Marquaire a, F. Montel b, L. Fusetti b
a
b

Laboratory of Reactions and Process Engineering, LRGP CNRS-UPR 3349, Nancy University, ENSIC, BP 20451, 54001 Nancy, France
TOTAL Exploration and Production, 64018 Pau Cedex, France

a r t i c l e

i n f o

Article history:
Received 3 January 2011
Received in revised form 11 March 2011
Accepted 21 March 2011
Available online 25 March 2011

a b s t r a c t
A mechanistic model consisting of 13,206 lumped free radical reactions has been developed to describe
the thermal evolution of a mixture of 78 alkanes: all n-alkanes from C1 to C32 and 46 branched alkane
model compounds from C4 to C32. The mixture was meant to represent the major part of the saturated
fraction of petroleum. The rate constants used are available from the literature. The lumping together
procedure is described and the model validated on the basis of several experimental results from the literature and relating to pure alkanes. The model is also compared to the saturated fraction obtained from
pyrolysis of Elgin oil at 372 C for up to 1000 h. The cracking global activation energy of n-C15 as well as
iso-C15 is close to 69 kcal/mol in the range 200350 C. The implications of the model for geological reservoirs will be discussed in a following paper.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
In exploration, the composition of petroleum in deeply buried
reservoirs (T > 200 C) is of strategic interest. Questions regarding
the availability of exploitable petroleum reserves in future decades
can only be answered if the thermal stability of liquid reserves can
be predicted under geological conditions. The thermal stability of
petroleum is commonly modelled using kinetic parameters determined from laboratory pyrolysis of whole crude oils (e.g. Ungerer
and Pelet, 1987; Ungerer et al., 1988; Bhar et al., 1992, 1997a,b,
2008; Schenk et al., 1997; Dieckmann et al., 1998; Lewan and Ruble, 2002; Lewan et al., 2006; Lehne and Dieckmann, 2007a,b) or of
pure hydrocarbons and simple mixtures. The experiments typically
use higher temperatures (300500 C) than those encountered in
reservoir rocks (80200 C), to compensate for geological time
(millions of years). Geological timetemperature conditions are
then applied to a kinetic model derived from experimental results.
Rate laws for the formation and destruction of hydrocarbons are
not easily obtained from experiments on the cracking of whole oils
because of the complexity of the chemical composition. This is easier when model compounds are used, i.e. pure hydrocarbons and
simple mixtures representing the reactivity families found in oil.
Alkanes are usually the most abundant class in non biodegraded
crude oils (Tissot and Welte, 1984). Pure n-alkanes have been
extensively studied to derive global kinetic parameters or detailed
free radical models (e.g. Ford, 1986; Weres et al., 1988; Domin,
1989; Domin et al., 1990; Song et al., 1994; Jackson et al., 1995;
Corresponding author. Tel.: +33 383175093; fax: +33 383378120.
E-mail address: valerie.vitzthum@ensic.inpl-nancy.fr (V. Burkl-Vitzthum).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.03.017

Bhar and Vandenbroucke, 1996; Bounaceur et al., 2002b). Except

for the work of Domin (1991) at very low conversion, to the best
of our knowledge, iso-alkane cracking has not been investigated
extensively. Bounaceur (2001) and Domin et al. (2002) rst proposed a free radical model taking into account a distribution of
n-alkanes from C1 to n-C30, similar to that found in the saturated
fraction of crude oils. Only ten individual branched alkanes were
included in their model as reactants, the branched alkanes being
formed via n-alkane cracking but not consumed afterwards. It
should be noted that their mechanism was based on a lumping together concept in order to keep the model to a reasonable size.
The purpose of the present work was to construct a model that
would be able to take into account the cracking of a complete distribution of n-alkanes, as well as of a distribution of branched alkanes from C1 to C32. A lumping together procedure similar to
that of Domin et al. (2002) was applied. Formation, as well as consumption, radical reactions for every alkane (linear or branched)
from C1 to C32 were included in the model. After justication of
the choice of model compounds for branched alkanes, the elaboration of the lumped free-radical mechanism is detailed and the
model validated on the basis of literature experimental data. Finally, the cracking of the distributions of n- and iso-alkanes characteristic of petroleum (Elgin oil, North Sea) is simulated and compared
with the experimental results. The implications of the model for
geological reservoirs will be discussed in a following paper.
2. Branched alkane model compounds
The structures of the branched alkanes in crude oils are so
numerous that most are included in the so called unresolved com-

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plex mixture (UCM). Most of the identied structures are monomethyl alkanes, particularly mid-chain isomers (Jackson et al.,
1986; Klomp, 1986; Fowler and Douglas, 1987; Hoffmann et al.,
1987; Kissin, 1987; Summons, 1987; Summons et al., 1988a,b),
but Kissin (1987) suggested that all monomethyl isomers can be
found in approximately the same amount. In the medium molecular weight (MW) range (C10C25), the most remarkable compounds
belong to the isoprenoid series and they frequently amount to ca.
1% of a crude oil, with pristane and phytane the most abundant
(Tissot and Welte, 1984). Components with n-alkyl branches longer than methyl also have been identied by several authors
(Kurashova et al., 1989; Gough and Rowland, 1990; Killops and
Al-Juboori, 1990; Gough et al., 1992; Warton et al., 1997).
Furthermore, it should be noted that in numerous biological
systems and sedimentary organic matter, some positions for the
methyl in monomethyl alkanes and their functionalised counterparts are favoured, particularly at C-2 and C-3 (Eglinton and Hamilton, 1967; Tornabene et al., 1970; Downing, 1976; Kolattukudy,
1976; Kaneda, 1977; Dowling et al., 1986; Shiea et al., 1991; Gunstone, 1996).
The goal of this study was to construct an alkane cracking
mechanism including all the n-alkanes from C1 to n-C32, as well
as branched alkanes from C4 to C32. Obviously, it was not possible
to take into account all the existing branched alkanes. That is why
we had to dene model compounds, at least one for each chain
length, on the basis of the previous observations.
All branched alkanes from C4 to C6 (Fig. 1) are included in the
mechanism in order to predict the composition of the generated
gas in detail.
For odd carbon numbers between C7 and C31, one model compound per chain length was chosen: the 2-monomethyl alkane.
This choice enabled us to represent one of the biologically favoured
methyl positions.
For even carbon numbers between C8 and C32, two model compounds per chain length were dened. The rst represents another
favoured methyl position, i.e. mid-chain. In addition to a biological
origin, branched alkanes are formed during alkane cracking via
addition of alkyl radicals to alkenes. Most are dialkyl alkanes with
the alkyl groups on neighbouring carbons, which are probably difcult to identify in crude oils because of analytical limitations. That
is why we chose dimethyl alkanes as the third type of model compound. In order to limit the number of elementary reactions, the
structures of the dimethyl alkanes, as well as the mid-chain monomethyl alkanes, were chosen to be symmetrical. The three types of
branched model compounds are summarized in Fig. 1.
Overall, the model comprises 32 n-alkanes and 46 iso-alkanes as
reactants.

Fig. 1. Model compounds for branched alkanes.

3. Elaboration of reaction scheme

It is now widely accepted that elementary free radical reactions
can adequately describe the thermal transformation of most species found in crude oils (e.g. Ford, 1986; Savage and Klein, 1988;
Weres et al., 1988; Domin, 1989, 1991; Domin et al., 1990,
2002; Jackson et al., 1995; Bounaceur et al., 2002a,b; Bhar et al.,
2002; Burkl-Vitzthum et al., 2004, 2005; Fusetti et al., 2010).
The proposed model includes 78 alkanes as reactants, each of
which can potentially undergo hundreds or thousands of free radical reactions. For example, the mechanism of n-C6 pyrolysis, at
only low conversion, comprises 156 reactions (Domin et al.,
1990) and includes 53 species (molecules and radicals). A detailed
model of our mixture at high conversion would thus require millions of reactions (the detailed mechanism of each pure alkane
and the related cross reactions) and the resulting computing time
would be unmanageable. Some simplication is therefore required,
which means that reactions and some species must be lumped together. The work is inspired by the previous models of Bounaceur
(2001) and Domin et al. (2002), but the method applied here is
slightly different. Indeed, the part of the mechanism concerning
n-alkanes in the model of Domin et al. (2002) was rst written
using an automated procedure and the number of reactions was reduced afterwards by lumping together radicals with the same
chain length and by lumping together some products as well. In
contrast, a lumping together procedure was applied immediately
in this study. All rate constants were derived from Allara and Shaw
(1980) or from the NIST Kinetics Database.
3.1. Unimolecular initiation
At high pressure (several hundred bar) and low or intermediate
temperature (200400 C), initiation rates are negligible vs. propagation rates (Bounaceur, 2001). Therefore all radicals formed by
initiation steps, whatever their structure, can be lumped together
in a single one and so, for each alkane, there is only one initiation
step in the model (Fig. 2). Simulations have enabled validation of
such an assumption.
For each alkane from C2 to C6, an average value of activation energy was estimated, and for C7+, the same value was taken, whatever the number of carbons in the molecule. Indeed for long
chain alkanes, the chain end effect can be neglected. Frequency factors are approximately proportional to the number of CC bonds. A
reference value was set according to the literature and all frequency factors were then calculated.

Fig. 2. Examples of each type of lumped free radical reaction.

V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

3.2. Decomposition via b-scission

In the mechanism, radicals are lumped together, i.e. the position
of the single electron is not precisely dened. For example, C3H7
represents the primary propyl radical as well as the secondary one.
However, since it is highly important to determine precisely the
products formed from each decomposition as well as the corresponding rate constant, each radical was un-lumped and its
decomposition precisely analyzed. For example the lumping together of the 2-methylbutyl radical (iso-C5) represents four different radicals depending on the position of the single electron. These
radicals undergo ve decompositions (Fig. 3) which are represented by three decompositions lumped together in the mechanism (Fig. 2) because some of them lead to the same products. It
should be noted that all alkenes with the same number of carbons
are lumped together in a single class. Moreover, the branched radicals included in the mechanism have the same structure as the isoalkane model compounds. Therefore, when a branched radical is
formed, it is replaced in the mechanism by the radical that has
the closest structure (example in Fig. 4).
The determination of the rate constants is a critical step: the
rate of a lumped reaction must be equal to the sum of the rates
of the reactions for which it stands; this means that, for the previous example, where the rst, third and fourth decompositions in
Fig. 3 are lumped together in the rst decomposition in Fig. 2:

ka isoC5 radical k1  1ary radical k3  3ary radical 2  k4

 2ary radical;

441

where 1ary stands for primary, 2ary for secondary and 3ary for
tertiary.
By implementing the intrinsic distribution of each type of
radical:

ka isoC5 radical k1  %1ary  isoC5 radical k3  %3ary

 isoC5 radical 2  k4  %2ary
 isoC5 radical
This leads to: ka = k1  %1ary + k3  %3ary + 2  k4  %2ary.
It should be noted that the second and fth decompositions in
Fig. 3 lead to different products and so cannot be lumped together
and remain un-lumped in the mechanism (Fig. 2, second and third
decompositions).
On the basis of the work of Bounaceur (2001), the intrinsic distribution of each radical was estimated (Table 1). Then, depending
on the type of decomposition, three reference rate constants were
set (Table 2) and the rate constant of every lumped decomposition
was calculated independently.
3.3. H transfer
H transfers between each alkane and lumped radical are included in the mechanism (Fig. 2). Activation energy depends on
the class (primary, secondary or tertiary) of the acceptor radical
and on the class of the carbon bearing the transferred hydrogen.
Reference values were estimated according to the literature (Table
3). An average value (1011 cm3 mol1 s1) was taken for the frequency factor of a single H transfer. In the mechanism, the H transP
fers are lumped and therefore: Alumped = Asingle, which implies
that Alumped is proportional to the number of H transfers the
lumped step stands for.
3.4. Addition
Average values for the activation energy and frequency factors
were estimated knowing that they are inversely proportional to
the number of carbons in the radical. It should be noted that every
C33+ radical formed by addition is lumped into a single class, whatever its number of carbons, which is considered as stable in the
model (Fig. 2).
3.5. Isomerization
Obviously, because of the lumping together of radicals, no isomerization reaction is explicitly written into the mechanism, but the
intrinsic distribution of each radical is implicitly taken into account
by way of decomposition rate constants.

Fig. 3. Detailed decompositions via b-scission on the example of iso-C5. For the rst
radical, two different bonds break, leading to different products. The arrow colour
corresponds to the breakage colour. (For interpretation of the references to colour in
this gure legend, the reader is referred to the web version of this article.)

3.6. Termination
Termination steps between all radicals were lumped together
(Fig. 2), because, like initiation steps, their rates are negligible vs.

Fig. 4. Replacement of a formed radical by the closest structure.

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V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

Table 1
Estimation of internal distribution of radicals (x is the number of secondary (2ary)
carbons and y, the number of tertiary (3ary) carbons).
Iso-CnH2n+2
56n67

Primary
radicals (%)

ary

7.5

9 6 n 6 15
16 6 n 6 22
23 6 n 6 29
n > 29

5
4
3
2

Tertiary radicals

ary

ary

2 % = (100-1 %)/
(x + 2y)
2ary% = (100-1ary%)/
(x + 1.5y)
Ditto
Ditto
Ditto
Ditto

7.5

n=8

Secondary radicals
(equidistribution)

ary

ary

%=22

% = 1.5  2

Alkane Cn 1-alkene Cn2

Table 2
Decomposition via b-scission: reference rate constants depending on type of CC
bond.
Frequency factor
(1013 s1)

Activation energy (cal/

mol)

1ary C2ary C
2ary C2ary C
2ary (or 1ary) C3ary
C

1.5
2.5
2.5

30,000
27,700
27,200

to n2

1-alkene Cn2

to n1

to n1

! Alkane-plus Cn2

to 2n1

3ary% = 1.5  2ary%

3ary% = 1.5  2ary%
3ary% = 1.5  2ary%
3ary% = 1.5  2ary%

Type of CC bond

Alkane Cn ! Alkane-minus Cn1

Alkylation equation:

ary

Cracking equation:

Table 3
H transfer: reference activation energy depending on type of radical and type of
transferred hydrogen.
Transferred hydrogen radical

CH4

CH3

CH2

CH

CH3
C2 H5
Linear
Branched

14,500
15,500
16,000

8200

12,900
13,500

9600
11,600
12,200
12,200

9600
11,600
12,200
12,200

propagation rates under our conditions. As a consequence, all termination steps lead to the same alkane and a reference rate constant was used. Our simulations conrmed that the
concentration of this end member alkane was negligible.
Neither cyclization nor aromatization reactions were included
in the mechanism because aromatics are negligible up to 50% conversion and the amounts remain low for higher conversions (Song
et al., 1994; Bhar and Vandenbroucke, 1996) even at high temperature (450 C). In previous studies (Bounaceur, 2001; Bounaceur
et al., unpublished data), it was shown that the importance of these
reactions with regard to alkane cracking decreases when the temperature decreases, and becomes minor below 300 C, particularly
at geological temperatures. Indeed, cyclization reactions require
the formation of alkenyl radicals by H transfer to an alkene, which
react further by way of intramolecular addition to form a ring.
There is a competition between these H transfers and the addition
of alkyl radical to alkene. The addition activation energy is from 3
to 5 kcal/mol lower than H transfer activation energy and so, when
the temperature decreases, the consumption of alkenes by addition
is favoured to the detriment of the cyclization route. So, cyclization
and aromatization reactions probably do not affect the n- and isoalkanes distribution to a signicant extent. Nevertheless, this
choice constitutes a limitation of the model.
Overall, the model comprises 13,206 free radical reactions and
193 species.
4. Stoichiometric equations corresponding to n- or iso-alkane
cracking
A free-radical mechanism such as the present one is based on
two generic stoichiometric equations (in moles):

where alkane-minus corresponds to an alkane whose molecular

weight (MW) is lower than the reactant and alkane-plus to an alkane whose MW is higher than the reactant.
Under our conditions [low temperature (200400 C) and high
pressure (1001000 bar)], addition to alkenes is fast, so both equations lead to (in moles):

2 AlkanesCn ! Alkane-minus Cn1

Alkane-plus Cn2

to n2
to 2n1

Indeed, the amounts of alkenes are low and become totally negligible at low temperature experimentally as well as in simulations,
as in petroleum (Tissot and Welte, 1984).
Moreover, in the mechanism, the formation of alkanes-plus is
due to the addition of alkyl radicals to alkenes. Because primary
radicals are negligible, alkanes-plus are mainly iso-alkanes.
So the above analysis leads to:
In the case of n-alkanes (in moles):

2 n-Alkanes n-Cn ! n-Alkane-minus n-Cn1

iso-Alkane-plus Cn2

to n2
to 2n1

In the case of iso-alkanes (in moles):

2 iso-Alkanes n-Cn ! n-or iso  Alkane-minusCn1

iso-Alkane-plus Cn2

to

to n2

2n1

Then, the produced alkanes react according to the same stoichiometric equations.
5. Pyrolysis of a pure n-alkane
The mechanism was tested on pure n-C15 as an example. The
model was simulated using the software CHEMKIN II (Kee et al.,
1989). Fig. 5 plots log xi (molar fraction of n- or iso-alkane Ci) vs.
the number i of carbons, after 1 week (low conversion) and after
15 yr (high conversion).
At low conversion, n-C15 obviously remains predominant. Alkanes-minus are mainly n-alkanes from C2 to n-C13 in almost the
same proportions. The formation of methyl radicals via decomposition by b-scission is slightly more difcult than for the other alkyl
radicals (Table 2). This is why the amount of CH4 is lower than the
amounts of C2C13. Furthermore, the decomposition via b-scission
of the C15 radicals cannot lead to the formation of a C14 radical, so
n-C14 cannot be formed primary: its amount is negligible. Alkanesplus are mainly iso-alkanes from C17 to C29. Indeed, alkanes-plus
are formed by addition of the predominant radicals that are the
C15 radicals, on alkenes comprising between C2 and C14 (decomposition via b-scission of C15 radicals). Moreover it should be noted
that n-alkanes-minus and iso-alkanes-plus are formed in the same
proportion, as illustrated by the above stoichiometric equation.
At high conversion, n-C15 does not predominate anymore. Distributions of n-alkanes and of iso-alkanes are obtained and the evolution of log(xi) vs. i is almost linear for i P 10. It should be noted
that methane is much less reactive than the other alkanes and
therefore it accumulates. The C33+ compounds accumulate but, as
mentioned above, this is an artifact due to the fact that their consumption is not taken into account in the mechanism. Furthermore, the amount of C2H6 is less than the amount of C3C10

V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

443

Fig. 5. Simulated product distribution obtained from n-C15 cracking at 350 C.

because it cannot be formed by addition, only by decomposition

via b-scission.
Finally it is important to note that, for i > 29, the aforementioned trend is not observed anymore. In the following paragraph
these break points are analyzed in order to understand whether
they have a chemical meaning or whether they are due to the
mechanism, which does not take into account the cracking of the
C33+ fraction.

Concerning iso-alkanes, to the best of our knowledge, few

experimental data are available at high pressure and intermediate
temperature (300400 C). We only found the results of Domin
(1991) relating to 2,4-dimethylpentane pyrolysis at 357 C,
210 bar and low conversion (up to 5%). Our model does not describe this alkane, but the corresponding lumped species is 2methylhexane. By comparing experimental 2,4-dimethylpentane
conversion to the simulated 2-methylhexane conversion (Fig. 10),
agreement was obtained.

6. Effect of number of carbons

7.2. Product distribution
In order to answer the previous question, a reduced mechanism
was written which comprises n- and iso-alkanes up to C27. Pyrolysis of n-C12 is simulated up to the same conversion extent as n-C15
previously. The product distributions show the same trends as for
the full mechanism, but the break points are moved to C24 (Fig. 6).
Therefore, these break points are linked to the maximum number
of carbons accounted for by the mechanism and have no chemical
meaning: this is an artifact of the mechanism, more precisely for
the C33+ compounds which are formed, but do not further react.
Hence, every conclusion relating to the longest alkanes has to be
taken with caution.
7. Experimental validation for pure alkanes as reactants
7.1. Conversion
The mechanism was tested on several pure n-alkanes with
chain length varying from 6 to 25, submitted to temperatures ranging from 300 to 450 C, pressures from 120 to 700 bar and conversions up to 94%. All the data were taken from the literature
(Domin, 1989; Song et al., 1994; Jackson et al., 1995; Bhar and
Vandenbroucke, 1996; Burkl-Vitzthum et al., 2004; Lannuzel,
2006; Lannuzel et al., 2010). The CHEMKIN II software uses the
perfect gas law to calculate the concentrations; consequently, for
each condition, the initial concentration was rst calculated separately by using the PengRobinson equation of state, in order to
evaluate the perfect gas pressure that leads to the same initial concentration. This pressure corresponds to the input value. Figs. 79
plot the conversion vs. time for all data. Agreement between the
experimental and the simulated conversions is observed for every
n-alkane and under each pressuretemperature-time condition.

Conversion is not the only parameter to be checked in order to

validate the model; product distribution also needs to be assessed.
Jackson et al. (1995) dened four fractions to describe the product
distribution (wt%) after n-C16 pyrolysis: C1C4, C5C9, C10C15 and
C16+. For each fraction, the experimental and simulated mass balances were represented vs. conversion. Data, at all temperatures
and pressures are gathered (Fig. 11). The composition of each fraction is well predicted by the model up to 30% conversion. Agreement between the experimental and simulated results is
satisfactory up to 50% conversion. Above 50% discrepancies appear;
in particular the C16+ fraction is overestimated and the C1C9 fractions are underestimated, whereas the C10C15 fraction is correctly
described, as well as conversion (Figs. 79). This can be easily explained as the C33+ species are lumped together in the mechanism
and, once formed, do not react further and accumulate at the expense of low MW compounds. This phenomenon only becomes
important at high conversion, which explains the observed
discrepancies.
Table 4 compares the simulated results with some data taken
from Bhar and Vandenbroucke (1996) who dened three fractions
after n-C25 pyrolysis: C1C4, C7C14 and C14+. As previously, at
intermediate conversion (37%) the agreement is totally satisfactory, whereas at high conversion (90%), the light alkanes are underestimated and the heavy ones overestimated.
8. Apparent activation energy
Values of apparent cracking activation energy in the case of
pure n-C15 and iso-C15 were calculated at several temperatures of
T0 between 200 and 350 C. In fact, the simulations were done at

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V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

Fig. 6. Simulated product distribution obtained by n-C12 cracking (reduced mechanism) and by n-C15 cracking (full mechanism) at 350 C: (a) linear alkanes and (b) branched
alkanes.

very short and constant conversion. The initial consumption rate r0

was calculated by using CHEMKIN, and by plotting ln r0 vs. 1/RT
(where R is the perfect gas constant and T the temperature in K)
with T = T0, T0  2, T0 + 2, the slope corresponds to the apparent
Ea. For both alkanes and whatever the temperature between 200
and 350 C, the apparent Ea was found to be constant and close
to 69 kcal/mol.
This value is consistent for n-alkanes with experimental Ea of nC25 (68.2 kcal/mol) determined by Bhar and Vandenbroucke
(1996) and used for the n-C14+ fraction by Vandenbroucke et al.
(1999) in their kinetic modelling of petroleum cracking. But in
the same model, for the other saturated C14+ fraction, which is
composed of cyclo- and branched alkanes, Ea is set to 59 kcal/
mol. Nevertheless, the authors concluded that it may be better to
group the n- and iso-alkanes on the one hand, and the cycloalkanes
on the other hand. The conclusion of Vandenbroucke et al. (1999)
appears to be justied on the basis of this study and of another
study of cycloalkane cracking (Bounaceur et al., unpublished data)
that showed Ea close to 55 kcal/mol at 200 C.
9. Saturated fraction of Elgin oil: comparison between
experimental and simulated results at 372 C
The mechanism was tested on thermal cracking experiments
involving a whole oil sample from the Elgin Field (North Sea,

UK). This sample has abundant saturated hydrocarbons and negligible polar compounds (Domin et al., 2002; Vandenbroucke et al.,
1999), making it well adapted to our model. Pyrolysis experiments
with the sample were conducted by ELF (TOTAL) in 19921993 but
the results were not published until now. The temperature was set
at 372 C, the initial pressure was ca. 400 bar, for several time periods up to 1000 h; the experimental conditions are summarized in
Table 6. Closed cells (20 cm3) were loaded with ca. 5 g Elgin oil and
added to the same oven at the same time. The C1C10 fraction was
analyzed using GCMS (gas chromatographymass spectrometry)
and the C11+ fraction was analyzed using GPC (gel permeation
chromatography) by applying the method of Synovec and Yeung
(1984), which uses toluene and tetrahydrofuran as solvents. The
product distribution (Fig. 12), e.g. log xi (xi molar fraction of all
hydrocarbons, n-, iso- and cycloalkanes as well as alkenes and aromatics) vs. the number i of carbons, was determined for several
time periods up to 1000 h. Nevertheless, it should be noted that
the n- and iso-alkanes represent more than 90% molar of the oil.
In order to test our mechanism, the molar composition of the
saturated fraction (Table 5) was deduced from the analysis. The
n-Ci/iso-Ci ratio is not known for i > 10 because GPC does not separate n-alkanes from iso-alkanes, so it was set to 0.5 according to
Vandenbroucke et al. (1999). This is an approximation as these
authors analyzed a different sample from Elgin Field, the composition of which is somewhat different due to inhomogeneity within

V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

445

Fig. 7. Comparison between experimental and simulated n-alkanes conversion from 299 to 357 C.

Fig. 8. Comparison between experimental and simulated n-alkanes conversion from 369 to 400 C.

the eld. The model was simulated using the mixture in Table 5 as
input composition, at 372 C and 400 bar; the product distributions
are represented in Fig. 13. A detailed comparison between Figs. 12
and 13 is complex because Fig. 12 includes all hydrocarbons
whereas Fig. 13 only represents n- and iso-alkanes. Nevertheless
the evolution of the distribution up to 1000 h appears satisfactory:
experimentally as well as via simulation, the evolution of the light
compounds is negligible, particularly up to 500 h and for i P 10 the
distribution follows a straight line whose slope increases with
time. To better characterize the evolution of the C10+ fraction, the

experimental and simulated average ratios of xi+1/xi with

15 < i < 25 were calculated for all time periods (Table 7). This ratio
is perfectly simulated up to about 200 h. However it stabilizes
experimentally from 200 h, whereas its decrease continues in the
simulation. The explanation of this apparent experimental stabilization remains unclear, but it may be because of cycloalkanes that
crack to alkanes and are not taken into account in the model. Comparisons of the evolution of the experimental and the simulated
molar fractions for individual alkanes show good agreement
(Figs. 14 and 15).

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V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

Fig. 9. Comparison between experimental and simulated n-alkanes conversion at 425 and 450 C.

Fig. 10. Comparison between experimental and simulated iso-C7 conversion at 357 C.

To conclude, all trends are well represented by the model and so

it is also validated in the case of a mixture as complex as an oil.
10. Conclusions
We have proposed the rst cracking model of n- and iso-alkanes
mixtures that represents their formation as well as their consumption. It includes all types of free radical reactions that can be reasonably expected to take place in the pyrolysis of alkanes below
450 C, except cyclization and aromatization reactions, but these
reactions are believed to be minor, especially at low temperature.
The rate constants for elementary processes have been estimated
on the basis of the literature and were not adjusted. The approach

is not empirical and uses reactions representing what happens at

the molecular scale.
Lumping together reaction types and species with similar structures and dening model branched alkanes allow limiting the
model to a reasonable size. The pyrolysis of a mixture containing
32 n-alkanes and 46 iso-alkanes is represented by 13,206 reactions
involving 193 species. Software like CHEMKIN II is able to solve
this system easily. The model was compared with several literature
experimental results with pure alkanes. With respect to conversion, the agreement is totally satisfactory but product distributions
are well simulated only up to 50% conversion. Above 50%, gas is
underestimated and heavy alkanes overestimated because of C33+
which, once formed, does not react further in our model. Moreover,

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V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

Fig. 11. Comparison between experimental (Jackson et al., 1995) and simulated product distributions (wt%) as a function of conversion.

Table 4
Comparison between experimental (Bhar and Vandenbroucke, 1996) and simulated
product distributions (n-C25 pyrolysis at 120 bar and 400 C over 3 and 15 h).
Product
fraction

n-C25 3 h 400 C 120 bar

n-C25 15 h 400 C 120 bar

Mass (%)
experiment

Mass (%)
simulation

Mass (%)
experiment

Mass (%)
simulation

C1C4
C7C14
C15+
C1C4
C7C14
C15+

1.1
28.9
69.7
1.1
28.9
69.7

1.7
24.4
78.4
1.7
24.4
78.4

8.8
41.7
46.6
8.8
41.7
46.6

0.6
10.3
89.1
0.6
10.3
89.1

the model was compared with the pyrolysis results for Elgin oil. In
this case, the global evolution of the saturated fraction is well represented by the model but a quantitative comparison is difcult.
Indeed, Elgin oil contains cycloalkanes and aromatics (<10%),
which are not included in our model. Nevertheless, we can conclude that the proposed model is globally validated by the experimental data.
For these reasons, the model can be tested at geological temperatures in a rather rigorous manner, in order to simulate the behaviour of oils in which the saturated fraction is predominant, like in
deeply buried reservoirs, although our model remains a simplistic
approximation of the true petroleum composition.
In a forthcoming study (Burkl-Vitzthum et al., unpublished
data), we propose to investigate if this new model leads to new insights into thermogenic gas generation and relative thermal reactivity of n- and iso-alkanes on a geological scale. These points are
also of importance concerning reservoir connectivity issues and
reservoir exploitation. For example, in the case of reservoirs under
deep seas, the low temperature leads to the precipitation of n-alkanes in tubing. We will investigate if our model permits reconstruction of the distribution of n-alkanes on the basis of the
distribution of iso-alkanes, and so if it leads to the calculation of

Table 5
Composition representing the n- and iso-alkanes distribution from Elgin oil.
Alkane

Mol.%

CH4
C2
C3
isoC4
nC4
isoC5
nC5
isoC6
nC6
isoC7
nC7
isoC8
nC8
isoC9
nC9
isoC10
nC10
isoC11
nC11
isoC12
nC12
isoC13
nC13

75.5
8.91
4.38
0.956
1.74
0.803
0.805
0.558
0.519
0.399
0.450
0.382
0.369
0.322
0.330
0.239
0.273
0.220
0.220
0.189
0.189
0.163
0.163

isoC14
nC14
isoC15
nC15
isoC16
nC16
isoC17
nC17
isoC18
nC18
isoC19
nC19
isoC20
nC20
isoC21
nC21
isoC22
nC22
isoC23
nC23
isoC24
nC24
isoC25

0.140
0.140
0.120
0.120
0.104
0.104
0.0890
0.0890
0.0766
0.0766
0.0659
0.0659
0.0566
0.0566
0.0487
0.0487
0.0419
0.0419
0.0360
0.0360
0.0310
0.0310
0.0266

nC25
isoC26
nC26
isoC27
nC27
isoC28
nC28
isoC29
nC29
isoC30
nC30
isoC31
nC31
isoC32
nC32

0.0266
0.0229
0.0229
0.0197
0.0197
0.0169
0.0169
0.0146
0.0146
0.0125
0.0125
0.0108
0.0108
0.00927
0.00927

Table 6
Pyrolysis conditions for Elgin oil.
Duration (h)
Oil wt. (g)
Temperature (C)
Initial pressure
(bar)

30
4.492
372
340

35
5.002
372
392

100
4.503
372
340

102
5.385
372
446

200
5.020
372
398

500
4.969
372
395

1000
5.051
372
395

the quantities of n-alkanes that would precipitate during reservoir

exploitation.

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V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

Fig. 12. Experimental product distribution of Elgin saturated fraction after whole oil pyrolysis at 372 C and 400 bar as initial pressure, up to 1000 h.

Fig. 13. Simulated cracking (372 C, 400 bar) of a linear-branched alkanes mixture in the same proportions as in Elgin oil.

Table 7
Comparison between experimental and simulated xCi+1/xCi molar fraction ratio
(average value from C15 to C25).
Duration (h)

Experimental xCi+1/xCi

Simulated xCi+1/xCi

0
30
100
200
500
1000

0.85
0.84
0.82
0.78
0.78
0.79

0.85
0.84
0.82
0.80
0.74
0.65

Finally, one major limitation of the model is probably the accumulation of the C33+ fraction at high conversion. One solution would be,
at each calculation step time, to extrapolate the alkane distribution on
the basis of the middle MW compound distribution and to compare
the extrapolation to the simulated results. The difference between
the extrapolation and the simulation corresponds to the accumulation which could be equally shared among the C1C32 alkanes for
the following step time. This method would avoid the accumulation
of C33+ as well as signicant deviation of the C1C32 distribution,
but its computational implementation remains unsolved.

V. Burkl-Vitzthum et al. / Organic Geochemistry 42 (2011) 439450

Fig. 14. Comparison between the experimental (in relation to the saturated
fraction) and the simulated molar fractions (%) of propane.

Fig. 15. Comparison between the experimental (in relation to the saturated
fraction) and the simulated molar fractions (%) of n-octane and C18.

Acknowledgements
We are grateful for valuable comments and suggestions from
C.C. Walters and an anonymous reviewer.
Associate EditorR. di Primio
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