Org. Geochem. Vol. 26, No. 3/4, pp.

281-287, 1997
Pergamon © 1997ElsevierScienceLtd
All rights reserved.Printedin Great Britain
PII: S0146-6380(97)00003-X 0146-6380/97$17.00+ 0.00

NOTE

Comparison of rate constants for some molecular tracers generated

during artificial maturation of kerogens: influence of kerogen type
F. BEHAR', Y. T A N G 2 and J. LIU 2
'IFP, Geochemistry Department, 1-4 avenue de Bois Pr6au, 92506 Rueil-Malmaison Cedex, France
2Chevron Petroleum Technology, 1300 Beach Blvd., Box 446, La Habra, CA 90633-0446, U.S.A.

(Received 13 June 1996; returned to author for revision 30 July 1996; accepted 20 December 1996)

Abstract--The purpose of this work is to carry out artificial maturation of various kerogens under iso-
thermal conditions in open and closed systems and to derive kinetic parameters for specific molecular
tracers such as n-Ct2 and n-C24 alkanes. Results show that individual normal alkane generation from
Type I and Type II kerogens follows first-order kinetics in both open and closed pyrolysis systems.
However, the normal alkanes generated from Type III samples do not follow a first-order mechanism.
For Type I and Type II kerogens, slightly different rate constants are obtained for n-C12and n-C24gen-
eration whereas for the two Type III kerogens, n-C24 is produced much faster than n-Ci2. Combining
the rate constants derived from open and closed system pyrolysis, Arrhenius plots were obtained for
the four samples under study from which accurate sets of kinetic parameters were calculated. © 1997
Elsevier Science Ltd

Key words--kerogen cracking, artificial maturation of kerogens, reaction mechanisms, kinetic par-
ameters, n-alkane generation

INTRODUCTION Parts of these previous results are, however,

Kerogen is the most abundant component of sedi-
mentary organic matter. As sediments are buried,
kerogen undergoes thermal cracking which leads to
petroleum generation. Further thermal degradation
of kerogen and/or petroleum produces gaseous
compounds. The prediction of both the quantity
and quality of hydrocarbons generated from a
given kerogen buried in a given sedimentary basin
remains a key problem in petroleum exploration.
The aim of the present study is to better con-
strain calculation of kinetic parameters according to
the following research strategy (Kagi et al., 1990;
Alexander et al., 1992; Tang and Behar, 1995)
• Choose a chemical class, or a set of individual
compounds, representative of the kerogen crack-
ing products which remains relatively stable in
order to minimize the overlap between primary
cracking and secondary reaction of the generated
compounds. We have selected n-alkanes as they
are important components of crude oils and are
well known to be the most thermally stable com-
pounds compared with the iso and cyclo alkanes
(Fabuss et al., 1964). We have selected the two
individual n-alkanes, Cl2 and C24, which are
found in all types of reservoir oils. We wanted to
extend previously reported work (Tang and
Behar, 1995) on n-el2 and n-C24 generation from
Toarcian shale kerogen to other kerogen types.
included in this paper for a comparative discus-
sion.
Since the key factor for determining activation
energy for hydrocarbon generation is the use of a
correct kinetic scheme, we have focused our
study on a better understanding of the reaction
mechanism for n-alkane generation. Thus, iso-
thermal conditions were selected for experiments
in open and closed pyrolysis systems.
SAMPLES
A Type I shale from the Green River Formation,
and two Type III coals from the Mahakam Delta
and the North Sea, respectively were selected with
maturities at the beginning of the oil window. Their
geochemical characteristics, including those of the
previously considered Toarcian Shale (Tang and
Behar, 1995) are summarized in Table 1. For both
shales and coals, kerogens were prepared by HF/
HCI digestion according to the standard procedure
described by Durand and Nicaise (1980).
EXPERIMENTAL
Open pyrolysis system
The open system experiments were carried out
using the Multiple Cold Trap Pyrolysis Gas

281
282
Table 1. Geochemical data for the studied samples (for Toarcian shale, data from Tang and Behar, t995)
Type Origin Tmax °C
1 Green River Finn. (Eocene shale) 438
II Paris Basin (Toarcian shale) 419
Ill Mahakam Delta (Miocene coal) 419
III North Sea (Jurassic coal) 429
Chromatography (MCTP-GC) instrument which
has been described elsewhere (Tang and Stauffer,
1993, 1994). About 6mg of dry kerogen were
loaded into a quartz tube (20 mm length, 2 mm i.d.)
plugged at one end with quartz wool, and placed in
the pyroprobe with a thermocouple in contact with
the sample. After a short purge cycle, the tempera-
ture of the pyroprobe was raised to 300°C for 6 rain
and any free hydrocarbon was vented through a
secondary valve. This valve was then rotated, and
the pyrolysis carrier gas (30 ml/min helium) was
diverted to the liquid nitrogen-filled cold traps.
As the sample was pyrolysed, the 22-port valve
advanced automatically at certain preset tempera-
ture or time points in order to capture the py-
rolysis products in the individual traps. When
the pyrolysis was finished, each trap contained a
thermal or time "slice" of the pyrolysate, frozen
and sealed at liquid nitrogen temperature. Each
trap was then sequentially drained of liquid
nitrogen, switched to the GC, and ballistically
heated to 300°C in order to send the sample to
the GC column for quantitative analysis.
Closed pyrolysis system
Pyrolyses were carried out at 120 bars in gold
tubes (40 mm length, 5 mm i.d. and 0.5 mm wall)
sealed by welding under an argon atmosphere and
containing ca. 100mg of dry kerogen per tube
(Behar et al., 1991). Temperature was measured
(accuracy _+ 2°C) by a thermocouple placed within
an empty tube in the autoclave. At the end of py-
rolysis, the autoclave was rapidly cooled (2 min) in
water to room temperature so that cooling time was
negligible relative to heating time. The tube was
pierced in dichloromethane, then cut in order to
recover the C7 + pyrolysis products and to evacu-
ate gases. For a good extraction efficiency, crushing
the insoluble residue in an agate mortar with
dichloromethane was needed prior to extraction.
After extraction for 1 h by stirring under reflux
then filtration, the dichloromethane extract was
injected into a gas chromatograph and n-Ct2 and n-
C24 quantified against an external standard which is
a distillation cut of saturates ranging between n-C~5
and n-C25.
Note
HI mg/g C VR % H/C at. ratio O/C at. ratio
945 n.d. 1.55 0.081
614 0.55 1.27 0.145
190 0.57 0.87 0.152
212 0.62 0.80 0.120
RESULTS AND DISCUSSION
Experiments were carried out under isothermal
conditions between 380 and 440°C in the open py-
rolysis system and between 300 and 350°C in the
closed pyrolysis system. For open system pyrolysis
experiments, the absolute amounts of n-Cj2 and n-
C24 are a combination of both n-alkane and o-
alkene pairs (Tang and Behar, 1995). In closed sys-
tem experiments, because the contribution of olefins
is negligible, the amount of n-Cl2 and n-C:4 corre-
sponds to n-alkanes only.
The key problem for assessing the order of the
reaction is the calculation of the conversion,
because it is necessary to know the amount gener-
ated at infinite pyrolysis time. Then, the conversion
can be calculated under any temperature/time con-
dition. Due to possible secondary cracking reactions
in closed system pyrolysis (Tang and Behar, 1995),
the rate constants were derived from experiments
carried out for temperatures below 350°C and at
350°C for experiments less than 24 h.
n-Clz and n-C24 generated from Type 1 and Type
II kerogens (data from Tang and Behar, 1995)
show good linearity of the first-order plot at the
temperature investigated under both open and
closed pyrolysis conditions. Figure 1 shows typical
examples obtained at 400°C for n-C~2. For the Type
I kerogen (Table 2), generation of both n-C~2 and
n-C24 is slower than for the Type II sample (data
from Tang and Behar, 1995 are reported in
Table 2). For each sample, the generation of n-C24
is faster than n-C~2 below 400°C but the rate con-
stant ratio n-Cz4/n-C12 decreases with increasing
temperature.
In contrast, for the two coals, a systematic devi-
ation from first-order was observed for the gener-
ation of the two n-alkanes, as illustrated in Fig. 1
f o r n - C 1 2 generation at 420°C for the Mahakam
coal. One observes at least two processes: a very
fast production, followed by a slower one. In order
to derive the rate constants for both fast and slow
reactions, we have to fit four variables (i.e. two rate
constants and two infinite values). Since the relative
rate constant values between the two reactions were
found to be at least one order of magnitude differ-
ent, we have chosen to use the classical deconvolu-
tion method to calculate the reaction parameters.
Based on a first-order plot, we first calculate the
rate constant of the slower reaction taking into
 Note 283

0 1000 2000 3000 4000 5000 6000

I I I

o -I'--.. ' ,;~e, o

1 n-c1 .4oo c
-0.4

41.6

-0.8

-1.0

-1.2

0 500 1000 1500 2000 2500

0;i ~ I i i

T y p e II
-o.5 - " ~ n'C12 at 400°C

-1.0 -

-1.5 -

-2.0

-2.5

0 1000 2000 3000 4000 5000

o r . i i i i i
o 5-] ~ T y p e Ill
"" I % n-C12 at 420°C
-1.0

-1.5

-2.0

-2.5

-3.0

-3.5

Pyrolysis Time (second} )=

Fig. 1. Examples of first-order plot of C~2 alkane generation from Type 1, Type II and Type I11
Mahakam samples under open system isothermal pyrolysis(for Type 11 kerogen, data from Tang and
Behar, 1995).
284 Note

Table 2. Rate constants for n-C~2 and n-C24 generated during tentatively knowing the good trapping efficiency o f
kerogen pyrolysis in open and closed systems under isothermal
conditions at various temperatures for the four samples under this kerogen network due to its high aromaticity
study (for Type II kerogen, data from Tang and Behar, 1995) and oxygen content (Behar and Vandenbroucke,
Kerogen T °C n-Ci2 (s-l) n-C24(s-t) n-C24/n-C12 1988). The fast reaction would correspond to ther-
mal desorption o f trapped saturates, whereas the
Type ! 350 7.08x 10 6 7.84x 104 1.11
380 5.72 x 10-5 5.73x 10-5 1.00 slow reaction would correspond to kerogen crack-
400 2.08 × 10-4 1.96x 104 0.94 ing and is the reaction to be c o m p a r e d with that o f
420 7.00 × 104 6.22x 104 0.89 Type I and Type II kerogens.
Type II 350 2.85 x 10-5 3.50 x 10-5 1.22 The results o f the calculated rate constant for the
380 2.47 x 104 2.72 x 104 1.10 slow reaction (Table 2) show that below 420°C, for
400 8.55 x 104 8.30 × 104 0.97
the two coals, the production o f n-C24 is much fas-
Type Ili ter than n-Cl2. The ratio o f n-C24/n-C12 rate con-
Mahakam 379 7.00 x 10-5 2.54 × 104 3.63 stants increases with decreasing temperature. It is
401 3.06 x 104 7.61 x 104 2.49
420 9.20 x 104 1.86× 10-3 2.02 still higher than 2 for temperatures between 415
and 420°C, whereas this ratio is below 1 for Type 1
Type III
North Sea 376 2.62 x 10 5 1.09x 104 4.16 and II kerogens.
396 1.11 × 104 3.55x 104 3.20 F o r each sample studied, Arrhenius equations are
415 3.55 × 104 9.70x 10-4 2.73
plotted in Fig. 2 for the generation o f both n-Cl2
and n-C24 in open and closed system pyrolysis, and
the corresponding kinetic parameters are given in
Fig. 3. F o r the two Type III samples, the a m o u n t s
account only long experiment durations for each o f n-Cl2 recovered at 350°C in the experiment o f
temperature. The rate c o n s t a n t for the fast reaction less than 24 h were too low to enable accurate de-
can then be calculated by the subtraction o f the termination o f the rate constant. As stated pre-
slow process from the early conversion. The advan- viously, it was not possible in closed system
tage o f this a p p r o a c h is to minimize any multiple pyrolysis to carry out experiments at higher tem-
solutions due to the non-linear fitting procedure. peratures because o f the possible secondary crack-
Unfortunately, there are not enough experimental ing o f n-C24.
data points at the very early cracking stages o f Due to the uncertainty o f our rate constant deter-
kerogen to get accurate values for the fast reaction minations, we estimated uncertainties on the acti-
rate constants. The occurrence o f these two reac- vation energy calculations to be 1 kcal/mol. This
tions for Type III kerogen may be interpreted only is in agreement with sensitivity considerations

TYPEI TYPEII
GREENRIVERSHALE -2 TOARCIANSHALE
On-C24 -4 -C24l
e n'C12
-7.5 -6
-6
-10 -10.
-12
0.0014 0.001450.00150.001550.0016 0,00165 0.0014
I / 1 I I
0.0015 0.0016 0.0017 0.0018
I I I

__= T Y P E III TYPEIII

NORTHSEA
I -s t MAHAKAMDelta • n-C12
-7.5 ~ ~n'C24 .5 t ~ n ' C 1 2 On-C24
-7.S
-10 -10
0.0014 0.001450.0()150.00'1550.0()160.00165 0.0014 0.001450.00150.001550.0016 0.00165
1/ T
Fig. 2. Arrhenius plots for n-C12 and rt-C24 generated during artificial maturation of the studied samples
in open and closed systems (for Type II kerogen, data from Tang and Behar, 1995).
 n-C,7
Note 285

n-C12 A=4.0E14(s "1) Ea= 56.3 Kcal/Mol Type I Kerogen

n-C24 A= 5.0E13(s "1) Ea= 53.6 Kcal/Mol
100

80

60

40
/
20

0
70 ab 9b 100 110 12o lao 14o 1so 1~o 17o
n-C12 A= 3.3E14(s "1) Ea= 54.6 Kcal/Mol Type II Kerogen
100
n-C24 A= 1.4E14(s "1) Ea= 53.0 Kcal/Mol

n-C24//
t-
O
80

60
/r-c1,
(I)
t- 40
O
0
20

0
70 ab 9b 16o 110 120 130 140 150 160 170
n-C12 A= 2.9E14(s "1) Ea= 55.5 Kcal/Mol Type III Kerogen
n-C24 A= 6.4E11(s "1) Ea= 46.1 Kcal/Mol
100

80

60
n/c / " 2

40

20

0
70 ab 90 100 l i 0 120 130 140 150 160 170
Termperature (°C)
Fig. 3. Predicted oil window for n-Cl2 and r/-C24 generated from the samples under study in natural
conditions with a sediment burial of 50 m/Myr and a geothermal gradient of 25°C/km (for Type II
kerogen, data from Tang and Behar, 1995).
286
reported by Burnham (1994). It is worth noting
that the same Arrhenius diagrams can be plotted
by combining the rate constant values obtained
in both open and closed system pyrolysis. This
enables one to increase the temperature range
investigated under laboratory conditions and thus
to get more accurate kinetic parameters.
Moreover, the success of Arrhenius plots for
both open and closed system pyrolysis indicates
that for n-alkane generation, there is no evidence
of a pressure effect.
For both Type I and Type II kerogens, the cross-
points of the Arrhenius diagrams of n-Cl2 and n-
C24 are in the same temperature range i.e. 390-
395°C. Although the discrepancy between the absol-
ute value of the activation energies and frequency
factors for n-C~2 and n-C24 are in the range of ex-
perimental error, for the two samples, the rate con-
stants obtained at low temperature for n-C24 will be
higher than that for n-Cl2. This is in good agree-
ment with what is observed on n-alkane distri-
butions in natural source-rock extracts (Tissot and
Welte, 1984).
For Type III samples, kinetic parameters for n-
C12 and n-C24 (Fig. 3) are significantly different. In
both cases, n-C24 activation energies and frequency
factors are lower than those of n-C12. When these
parameters are extrapolated to geological conditions
(Fig. 3) assuming, for instance, sediment burial of
50 m/Myr and a geothermal gradient of 25°C/kin,
the n-alkane window will be much enlarged com-
pared with those of Type I and Type II kerogens.
This is consistent with data published by Tang et
al. (1996). Their study indicates that the ratio
between n-Cl6 and n-C30, for a large number of
coal extracts from various basins, could increase
dramatically with maturity. This means that as far
as n-alkanes are concerned, a very early generation
of the heavy compounds can occur at temperatures
as low as 110°C. Nevertheless, a significant amount
of these compounds may not be expelled due to the
retention capability of the coal structure (Behar and
Vandenbroucke, 1988). The generation window
between n-C12 and F/-C24 will be within 35°C for the
Type III samples and only within 7 10°C for the
Type I and Type II kerogens.
CONCLUSION
Artificial maturation of three reference kerogens
was carried out in open and closed pyrolysis sys-
tems under isothermal conditions in order to com-
plete the experimental determination of the kinetic
parameters on molecular tracers, such as n-C~2
and n-C24. For Type I and Type II kerogens, first-
order plots can be obtained for the generation of
the two n-alkanes in open and closed system py-
rolysis. Although n-C24 generation for both Type I
Note
and Type II kerogens is faster than that of n-Ci2,
their activation energies are very close to each
other. However, for Type III samples, significant
differences were observed for the rate constant
values between n-Cl2 and rI-C24 generation: the
ratio n-C24/n-Ct2 being between 2.02 and 4.16
compared with 0.89 and 1.10 for Type I and Type
II kerogens when pyrolysed in the same tempera-
ture range (380-420°C). Whatever the kerogen
type, Arrhenius diagrams were obtained combining
the rate constant values calculated from exper-
iments in open and closed system pyrolysis. For
Type I and Type II kerogens, the frequency fac-
tors obtained for both n-Cl2 and n-C24 are in the
same range, whereas they are very different for the
two coals. When kinetic parameters are extrapo-
lated to geological conditions, the generation win-
dow of n-alkanes could be as large as 35°C for
Type III and only 10°C for Type I and Type II
kerogens.
The kinetic study of molecular tracers seems to
be a useful tool for a better constraint in the
search for frequency factor values in the standard
methods for calculating kinetic parameters.
However, these molecular tracers are present in
very low amounts in the products of kerogen
cracking. It should be interesting to apply such an
approach to any GC amenable compound repre-
sentative of the main chemical classes found in
petroleum reservoirs.
Associate Editor - - A. G. Douglas
Acknowledgements M. Vandenbroucke is gratefully
acknowledged for her helpful comments.
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