Advances in OrganicGeochemistry1989

Org. Geochem. Vol. 16, Nos 1-3, pp. 49-60, 1990 0146-6380/90 $3.00 + 0.00
Printed in Great Britain.All rights reserved Copyright© 1990 PergamonPress plc

A new method for the measurement of kinetic parameters of

hydrocarbon generation from source rocks
U. C. KLOMPl and P. A. WPaOHr 2
~Shell Thornton Research Centre, Chester, Cheshire CHI 3SH, U.K.
2Koninklijke/Shell Exploratie en Produktie Laboratorium, Volmerlaan 6, 2288 GD Rijswijk,
The Netherlands

(Received 20 September 1989; accepted 20 March 1990)

Al~ltact--A new laboratory technique for the determination of the kinetic parameters of hydrocarbon
generation has been developed. It measures separately the reaction fate's dependence on the temperature
and on the degree of kerogen conversion. The method allows the direct determination of the activation
energy of generation and makes no assumptions about the pre-exponential factor or the reaction order.
The kinetic parameters of hydrocarbon generation from source rocks of the major kerogen types have
been examined. There are wide variations in the isothermal reaction rates; measured activation energies
lie mainly in the range from 46 to 56 kcal/mol (190-235 kJ/mol). The differing kinetic behaviour is
compared with the elemental compositions of the kerogens.
Using a numerical integration method, the kinetic data can be extrapolated to geological heating rates
and compared with estimates of conversion for naturally mature source rock samples.

Key words--hydrocarbon generation, pyrolysis, reaction kinetics, activation energy

INTRODUCTION conversion data are also included in the optimisation

Predicting the timing of hydrocarbon charge in sedi-
mentary basins on the basis of experimentally derived
kinetic parameters for hydrocarbon generation from
immature source rocks has achieved widespread
acceptance in recent years. The commonest kinetic
model assumes that the kerogen liberates primary
cracking products through simultaneous first-order
reactions that have the same pre-exponential factor
and a certain distribution of activation energies
(Tissot, 1969; Tissot and Espitalie, 1975; Ungerer and
Pelet, 1987; Tissot et al., 1987). Both the frequency
factor and the activation energy distribution are
refined to match reaction rate data collected as
kerogen samples are heated non-isothermally at
widely different rates. Similar methods assume simple
(e.g. Gaussian) distributions of activation energies
and pre-exponential factors (Anthony et al., 1975;
Juntgen and van Heek, 1979; Quigley and Mackenzie,
1988). An alternative treatment of non-isothermal
pyrolysis data collected at different heating rates
(Friedman, 1963) assumes that the reaction rate is a
function of the conversion and temperature only and
not of the temperature history. The activation energy
is determined as a function of conversion, and no
assumptions are required about the pre-exponentiai
factor. Other methods involve semi-open or closed
system pyrolysis, sometimes including secondary
cracking and evaporation in the pyrolysis schemes
(Burnham and Braun, 1985; Lewan, 1985). A com-
parison of some of these methods is given by Burn-
ham et al. (1987, 1988). Where available, natural
(Tissot et al., 1987; Quigley and Mackenzie, 1988)
and, although they are often imprecise, they provide
an important means of constraining or checking the
kinetic parameters.
In this paper we present the results of a kinetic
method that measures rate and activation energy
directly in the laboratory as separate functions of
kerogen conversion, without requiring assumptions
about the reaction order or the frequency factor. A
numerical integration method makes it possible to
extrapolate the kinetic data to any temperature his-
tory, in particular those of source rocks in nature. As
well as performing kinetic analyses on a variety of
source rocks of different kerogen types, the compo-
sitions of the pyrolysates are monitored by elemental
analysis. The generation kinetics are compared with
data from a natural source rock system to check the
validity of the method.
THEORY OF THE KINETIC METHOD
The rate of a chemical reaction is often expressed
by the general kinetic equation
Rate(T, x ) ffi ( dx /dt )r. x
=A(x)" exp[-E(x)/RT]. [1 - x] n, (1)
where T is the absolute temperature, [1 - x ] is the
reactant concentration, n is the order of the reaction,
and A and E are, respectively, the frequency factor
and the activation energy. In the case of the trans-
formation of kerogen to hydrocarbons, x is the mass

49
50 U.C.KLoMPandP.A.WRIGHT
fraction of the total potential hydrocarbon gener-
ation that has been generated at time t; [1 - x] is then
the fraction of unreacted, but reactive, kerogen.
Equation (1) is best regarded as a convenient
formulation of the generation rate's dependence on
temperature and degree of conversion. In the kinetic
method we use, the activation energy and rate are
determined directly as separate functions of kerogen
conversion, thereby avoiding both the need for non-
linear regression in determining the activation energy
and the need to assume a functional form for the
dependence of rate on conversion (no reaction order
is assumed). The generation rate is measured as the
source rock is heated at a constant temperature (Tm~t)
between 300-350°C. The rate may then be expressed
as an empirical function of the conversion:
Rate(Treat, x) = krm.,(x) "frm.,(X). (2)
The activation energy is then measured by follow-
ing the reaction rate as the temperature is increased
in steps of 10°C. Relating the rate at each tempera-
ture to that at a reference temperature (Trot) at the
same conversion,
Rate(T, x) = Rate(Tref, x). exp[-E(x)/RT]
x exp[E(x)/RT~f], (3)
a measurement of the activation energy can be made
by regression of the equation
Rate(T, x) = Rate(Tr~f, x)
xexp{-[E(x)/R].(l/T- 1/T~f)} (4)
or, more correctly, by a linear regression of
In(Rate(T, x )/Rate( Trcf, x ))
=[E(x)/RT,~I-[E(x)/R]. I/T. (4a)
An example of the method is given using a Kim-
meridge source rock of natural maturity estimated
at 0.64% VRE (vitrinite reflectance equivalent).
Figure I, shows the signal plotted vs time for the just
mature source rock heated at 340°C, which can then
be converted into a plot of a normalised rate vs
conversion (Fig. 2). This latter plot represents the
empirical function of rate as a function of conversion,
Rate(Tin=, x) of equation (2). A measurement of the
apparent order of the reaction can be made from the
isothermal rate vs conversion data. A rearranged
form of equation (1),
In(Rate) = In k + n ln[l - x], (5)
gives a plot whose slope gives the apparent reaction
order. In fact, the plots of these variables often show
curvature, particularly at low and high conversions,
indicating that the apparent order, the activation
energy, the pre-exponential factor or combinations of
all three are dependent on the conversion. To enable
the rate's decrease with conversion to be parameter-
ised, the apparent order was calculated by linear
regression of equation (5) for conversions from 0.20
25.
lO
-i o 60 i~ 200 2~o
Time at 340=0 (h)
Fig. 1. The FID signal vs the time of isothermal maturation
at 340~C for a just mature Kimmeridge source rock. The
area A 2 (which equals the time integral of the FID signal
between the start of the experiment and time t) is pro-
portional to the amount of hydrocarbons produced up to
time t. The constant area A~ + A2is proportional to the total
amount of hydrocarbons produced. Therefore, at time t the
conversion is defined as the ratio A2/Am+A2. Conse-
quently, the rate of conversion corresponds to the derivative
of the ratio with respect to time, which equals the FID signal
divided by Aj + A 2.
to 0.80. For the just mature Kimmeridge source rock
this gave a value for n of 1.56. The apparent reaction
order measured in this way, which will depend on the
temperature at which it is determined if the activation
energy varies as a function of conversion, gives
no information on the reaction order of individual
reactions which may be occurring with a range of
different kinetic parameters; it cannot be used in
direct extrapolation to geological temperatures.
To determine the activation energy of generation,
the rate must be measured as a function of tempera-
ture without changing the degree of conversion. To
this end, at different states in the isothermal heating
(and therefore at different conversions which may
later be calculated from the complete signal vs time
plot) the temperature is rapidly lowered well below
the isothermal maturation temperature and then
raised stepwise, allowing enough time for a measure-
ment of the rate at each temperature (Fig. 3). The
0.05
q
"7
0.04
C
0
•~ 0.03
0
0
I 0.02, Oo O
"6
Oo
~0.01
0,00 , o ~
0 012 014 0.6 0.8 1
Conversion at 340°C
Fig. 2. The normalised rate of conversion (per hour) vs the
conversion as calculated from the data of Fig. 1.
 Measurement of the kinetic parameters of hydrocarbon generation
•4 ~ ltme
Fig. 3. The FID signal obtained while measuring the effect
of temperature on the rate of hydrocarbon generation for
the Kimmeridge source rock. This experiment consists of
nine steps each lasting 25 min. During the first 10 rain the
background (B) of the FID is measured while the rate of
hydrocarbon generation is measured for the last 15 min in
each cycle. At the start of each step, the temperature is
increased rapidly by about 10°C. The numbers on top of the
curves denote the final temperature for each step. Above
291.8°C the FID signal is attenuated by a factor of 2 with
respect to the preceding step.
time steps and temperatures are chosen so that the
change in conversion during the determination of an
activation energy is very small, less than around 3%
at conversions greater than around 10%. (It is
difficult to measure activation energies at very low
conversions because of the very high rates of conver-
sion. In addition to conversion, these high rates may
reflect desorption of unextracted bitumen or tightly-
bound solvent). To a good approximation, then, the
activation energy is determined at a single conver-
sion. The activation energy is, in practice, determined
from an Arrhenius plot (Fig. 4) that is the linear
regression of equation (4a). By repeating this tem-
perature program at different stages in the matu-
ration, the activation energy is determined as a
function of conversion (Fig. 5).
Legend
10 _ • 8.3 h 340"C
[] 28.3 h 340"C
t~ --,,!, I. se.s h 3~0C
o ~ 0 135.3 h 340"C
6 o : ~ -~.Ok~L~mo,
In
v 0 • []
c 4
o • []
0 •
1.6o 1.~5 1.~o i.~s 1.~o 1.~
lOOO/1"
Fig. 4. Arrhenius plots of the logarithm of the rate of
hydrocarbon generation (FID signal ) at temperature T vs
the reciprocal absolute temperature. The activation energy
is thus determined at four different stages of isothermal
maturation.
51
55.
[] []
v
• []
• •
g
8 []
• Tm=310°C
[] Tm=340°C
o o12 014 o:6 o'.e
Conversion
Fig. 5. The activation energy, determined during different
isothermal heating experiments with maturation tempera-
tures of 310 and 340°C, plotted as a function of conversion.
Once both the rate (Trot) and the activation energy
E have been determined experimentally as a function
of conversion, the source rock conversion can be
calculated at any stage during source rock burial by
means of numerical integration when the temperature
history is known. An estimate of the VRE maturity
of the source rock can also be made using a modifi-
cation of the Lopatin method, where, in place of the
factor 2 for the rate increase per 10°C, a factor was
used which improved the fit of a natural data base of
vitrinite measurements and related burial histories
when calibrated on a single VR vs TTI line. Plotting
calculated conversion of the kerogens against esti-
mated VR allows source rocks with different geologi-
cal histories to be compared. It was felt that for the
purposes of this paper the VRE maturity was a
convenient and interesting axis for the comparison of
the different source rock types, notwithstanding the
additional errors that may be included by modelling
the VR at the same time as the conversion.
The key assumptions made by this method are that
reactions proceed in the same sequence at different
temperatures and that the measured activation ener-
gies are close to the true activation energies of the
cracking process and are not apparent values result-
ing from the superposition of a wide variety of
reactions of different activation energies (which might
also have different pre-exponential factors). If, say,
reactions with activation energies of 40-60 kcal/mol
were responsible for the conversion, then upon arti-
ficial maturation at different isothermal tempera-
tures, lower temperatures would initially favour
-'~ lower activation energies relative to higher tempera-
tures, leaving higher energy reactions over at higher
0
conversions. Experiments show that the measured
activation energies during maturations at 310 and
340°C are, within error, the same. In addition, if a
1.6o
very wide spread of activation energies were respon-
sible for hydrocarbon generation, then the lower
temperatures of natural maturation would greatly
favour the reactions of low activation energy and
reactions of much higher activation energy would be
left. In practice, activation energies in naturally
52 U. C. KLOMP a n d P. A. WRIGHT

Table 1. The maceral description of the immature samples examined; estimates of the maturity (VRE) of the samples are also
given where available
Sample VR(E) S.O.M. Vitr. 1 Vitr. 2 Sp/Cut Sub. Res. Lipdet. Algae
Type I
Torbanite, Australia 17 7 0 3 0 0 2 70
U.S.A., Green River Fm. 0.55 59 0 0 0 0 0 17 23
Thailand-I 0.55 26 0 3 0 0 0 35 36
Thailand-2 0.55 50 0 5 0 0 0 15 30
Gabon 42 0 0 0 0 0 12 46
Type I1
Kimmeridge-2, U.K. 0.55 60 0 0 12 0 0 16 12
Hanifa, Qatar 0.6 65 0 0 0 0 0 18 18
Monterey-l, U.S.A. 0.38 100 0 0 0 0 0 0 0
Monterey-2, U.S.A. 0.47 100 0 0 0 0 0 0 0
Type Ill
Sarawak- 1 0.43 0 2 83 1 2 5 5 0
Sarawak-2 0.,16 0 5 72 1 16 2 `1 0
Sarawak-3 0.`18 0 5 79 0 10 3 3 0
Sarawak-4 0.,19 0 22 65 0 5 5 3 0
Indonesia-1 0.69 0 78 13 2 0 1 5 0
Indonesia-2 0.57 0 15 68 3 3 3 5 0
Indonesia-3 0.6 0 18 65 5 2 3 ,1 0
Netherlands 0.6 0 1,1 75 9 0 0 0 0
Abbreviations: S.O.M.--structureless organic matter; Vitr. l--Vitrinite 1 (telinite + telocolfinite); Vitr. 2--vitrinite 2 (desmo-
collinite); Sp/Cut-----sporinite +cutinite; Sub.-----suberinite; Res.--resinite; Lipdet.--liptodetrinite. The visual percentages
estimated in the source rock have been normalised to 100%.

mature source rocks are usually close to those ob-
served in the later stages of artificial maturation of
immature source rocks.
EXPERIMENTAL METHOD
Source rock samples are finely ground to a grain
size of no larger than about 150/tm and placed for
1 week in a Sohxlet apparatus, where bitumen is
extracted with chloroform/methanol. The samples
are then dried at 100°C under 200mbar nitrogen.
50-200 mg of the source rock are put in a stainless-
steel sample chamber (40mm long with i.d.=
2.7 ram) and heated overnight in a modified gas
chromatography oven in 10 cma/min of flowing nitro-
gen at 150-200°C to remove the remaining solvent.
Pyrolysate that is volatile at the experimental tem-
peratures (260-360°C) is measured by a flame ion-
isation detector (FID). By switching the flow of
carrier gas through the sample chamber away from
the FID detector, a background signal can also be
measured. The temperature remains stable to 0.3°C,
as measured by PT100 resistance thermometers in-
serted into each sample chamber less than 1 cm away
from the sample. Measured temperatures at different
positions within the oven may vary by up to 2°C,
but remain constant at each position. The PTI00
thermometers are used as supplied (random in-house
calibration up to 200°C with a quartz reference
thermometer showed that the PTI00s gave tempera-
tures within 0.3°C of the quartz thermometer).
The temperature is increased in steps to the isother-
mal maturation temperature, and this initial signal/
time history is later converted to expected signal and
time at the maturation temperature. In the activation
energy determination, the temperature is first reduced
and the sample is given 2 h to reach a steady state
(allowing all the volatile bitumen generated and not
expelled at the higher temperature to be removed).
For the temperature increase, steps of 40 min were
usually enough for the signal to reach a steady value.
(Because of the relatively slow rates of conversion the
generation rate at each temperature is approximately
constant.) The highest temperature of the stepwise
increase is arranged to be the maturation tempera-
ture, so that after the stepping the isothermal matu-
ration is continued. The time spent in the activation
energy determination is converted to an effective
maturation time at the isothermal temperature by
assuming a doubling of rate with each 10°C rise in
temperature and thus dividing the actual time spent
in each step by a factor 2(rm'- ~/:0, where Tm,t is the
isothermal maturation temperature and T is the
temperature of the step.
At the maturation temperatures usually adopted,
an experiment takes from 2 to 3 weeks. Temperature
programming and data collection are fully auto-
mated. The sample yield is measured before and after
heating to determine the final conversion.
It should be noted that the experimental method
limits the kinetic analysis to products that are volatile
at temperatures between 260-360°C. In practice, this
corresponds to compounds with boiling points as
high as those of normal C30-C40 alkanes. For less
volatile hydrocarbons the measured kinetics may be
rate-limited by evaporation. Our measured kinetics
will therefore apply to the generation of medium to
high API gravity oils rather than to heavy oils.
Kinetic measurements have been performed on a
variety of immature source rocks of different kerogen
types, for which standard pyrolysis and maceral data
were available (Tables 1 and 2). For comparison, the
kinetics of some naturally mature source rocks have
also been determined. In addition, the composition
of the pyrolysate was determined by an elemental
analysis that combined pyrolysis and combustion
 Measurement of the kinetic parameters of hydrocarbon generation 53

Table 2. Pyrolysisdata on sourcerocks and coals selectedfrom those of Table 1

Sample label TOC TmaA Cpyr/Ctot (S/C)ker (S/C)pyr (H/C)ker (H/C)pyr
Type I
Torbanite 60.0 492 0.74 0.003 0.004 1.42 1.86
U.S.A. 8.9 476 0.79 0.014 0.017 1.48 1.68
Thailand-I 12.2 480 0.75 0.003 0.005 1.40 1.79
Gabon 10.2 473 0.71 0.006 0.009 1.33 1.72
Type I1
Kimmeridge-I 13.8 461 0.66 0.032 0.048 1.32 1.80
Hanifa 2.4 461 0.73 0.054 0.075 1.16 1,56
Monterey-I 2.2 435 0.65 0.055 0.084 1.20 2.00
Monterey-2 8.6 452 0.70 0.048 0.069 1.28 1.70
Type III
Sarawak-1 59.1 461 0.25 0.002 0.008 0.88 2.62
Sarawak-4 65.7 463 0.22 0.002 0.012 0.83 2.92
Netherlands 47.0 467 0.29 0.003 0.011 0.90 2.46
TOC is the total organiccarbon percentage, and T~x is the temperature of the maximumsignal during
non-isothermalpyrolysisat 30°C/rainmeasuredby a K-couplethermometerin contact with the sample
(reproducibilityto within 2°C). All of the other parameters were determinedduring non-isothermal
pyrolysisof isolated kerogensor coals followedby combustionin accordancewith the method of van
Leuvenet aL (1988).Cpyr/Ctot is the ratio of carbonevolvedduringpyrolysiscompared with the total
organic carbon, (S/C)ker and (S/C)pyr are the atomic organic S/C ratios of the kerogen and the
pyrolysate,respectively.Similarly,(H/C)kerand (H/C)pyr are the atomicH/C ratios of the kerogenand
pyrolysate.

with a mass spectrometer, in accordance with the
method of van Leuven et al. (1988). Kerogen isolates
and coals were analysed using a heating rate of
200°C/rain up to 1000°C, followed by combustion.
During pyrolysis, two sulphur peaks are observed;
the first comes from organic sulphur, the second from
pyrite decomposition. Carbon, hydrogen and sulphur
atomic ratios are given in Table 2, split up into total
and pyrolysate compositions.
RESULTS
The results for each source rock's reaction kinetics
are summarised in plots of the isothermal generation
rate and the activation energy, both measured as a
function of conversion (Figs 6-8). Although iso-
thermal maturation took place at temperatures be-
tween 310-360°C, according to the thermal reactivity
of the source rock, all rate data are converted to a
standard temperature (340°C) to facilitate compari-
son. Apparent reaction orders were calculated for
rate data at conversions between 0.2-0.8.
Using a numerical integration method, the con-
version curves of each kerogen type were calculated
and plotted against an estimate of the VR assuming
a heating rate of 3.3°C/my. The VR rather than
temperature was plotted on the x-axis to enable the
comparison of source rocks with different burial
histories.
The atomic sulphur/carbon ratios of pyrolysates as
a function of conversion determined by pyrolysis--
combustion-mass spectrometry are displayed in
Fig. 9.
Type I
The source rocks from the U.S.A., Thailand and
Gabon are composed predominantly of structureless
algal organic matter (algal S.O.M.), with recognisable
algal remains, whereas the torbanite from Australia
is made up largely of recognisable Botryococcus
algae.
A first-order reaction with a single activation
energy would appear as a straight line on the rate
vs conversion plots. The algal S.O.M. source rocks
(see Fig. 6) in fact, approximate this behaviour.
This near first-order behaviour [n (apparent) = 1.3 to
1.6] may be explained by the kerogens' chemical
homogeneity and their low sulphur content. At
very low conversions they have higher reaction
rates, though, since residual solvent or bitumen
is removed particularly in the first few percent of
conversion.
The highly structured, algal torbanite sample
converts much more slowly than the other Type I
samples. The isothermal rate at lower conversions is
lower than a first-order model would predict--the
apparent reaction order is 0.71.
Activation energies for generation from the Type I
source rocks vary from 49 to 55 kcal/mol; most of the
generation occurs with values at the lower end of this
range. Average values from the torbanite are at the
upper end of this range (52.5-55 kcal/mol). These
measured values are in reasonable agreement with
those measured elsewhere (Campbell et aL, 1978;
Ungerer and Pelet, 1987).
In general, the pyrolysates of Type I source rocks
were very low in sulphur (total S/C < 0.02; see
Table 2 and Fig. 9).
Type I source rocks are predicted to generate a
sulphur-poor product over a narrow maturity inter-
val, which for the kerogens containing poorly struc-
tured organic matter is mainly from 0.75 to 1.0 VRE,
with a peak generation rate, assuming linear heating,
at 0.85-0.9VRE. The torbanite, which generates
more slowly than the other, less-structured algal
source rocks, is predicted to generate at a higher
maturity (1.0-1.2 VRE).
54 U. C. KLOMPand P. A. Wmorrr

Source Rock Transformation rate at 340°C

USA Thailand and G a b o n Torbanite

°f.!°°.
• Thai-1 oThai-2 •Gabon

0.02 0.02 0.005

0 , / "=,~ 0 0 , , -
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 1
Conversion Conversion Conversion

Measured Activation Energies

• Expt.-1 • Expt.-3
° Expt.-2 o Expt.-4 • Thai-1 o Thai-2 . Gabon • Expt-1 n Expt-2 • Expt-3
60
B
O

50
Q
% O° •
~e
• °'D, ,~ .= ~o 60s0 t ""° .eo. l
LU

40 40 , , 40/ , ,
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
Conversion Conversion Conversion

¢-

.o
1/ /
0.5
Calculated Yield Curves for Total Hydrocarbon

0.5
Thai-1 Thai-2 Gabon
Generation

0.5

0 0 q i i 0 n n r i

0.4 0.6 0.8 1 1.2 1.4 1.6 0.4 0.6 0.8 1 1.2 1.4 1.6 0.4 0.6 0.8 1 1.2 1.4 1.6
Estimated vitrinite reflectance Estimated vitrinite reflectance Estimated vitrinite reflectance

Fig. 6. Plots of the reaction rate per hour at 340°C (standardised to the expected rate at 340°C using
measured activation energies when the actual isothermal maturation temperature used was not 340°C) and
the activation energy, both as a function of conversion. The samples are the fine ground, extracted
immature Type I source rocks of Tables 1 and 2. Using these kinetic data in a numerical integration
method, the expected conversion is calculated assuming a heating rate of 3.3°C/my and plotted against
an estimate of the VR level, as calculated using a modified Lopatin method.

Type H which may be attributed to their higher sulphur

For immature source rocks of Type II, which are
made up of bacterially transformed S.O.M., a wider
range of kinetic behaviour is observed than for the
Type I S.O.M. samples (Fig. 7). In particular, the
Monterey samples have higher initial rates of gener-
ation. The marked curvature of the isothermal rate
plots indicate a higher apparent reaction order, which
is between 1.9-2.4 for all except the Monterey-1
sample, for which it is 3.4. The activation energies
measured vary from 46 to 55 kcal/mol, usually show-
ing a gradual increase with conversion. All source
rocks show higher reaction rates than those of Type I,
content. The S/C ratio is seen to fall off rapidly with
conversion (see Fig. 9).
A naturally matured and partly converted Hanifa
source rock (VRE=0.78) was also examined
(Fig. 10). The natural conversion of this sample is
estimated at 60% from Rock Eval measurements (see
below). The reduction in the reaction rates and
apparent order as well as the high activation energy
(around 53 kcal/mol) is consistent with a lower
proportion of weak bonds at high maturities.
The Type II source rocks start to generate
hydrocarbons earlier than those of Type I (usually
 Measurement of the kinetic parameters of hydrocarbon generation 55

S o u r c e R o c k T r a n s f o r m a t i o n rate at 3 4 0 ° C

Kimmaridge Fm, UK Hanifa Fm, Qatar Monterey Fm, USA

= Sample-1 . Samlde-2 ,, Sample-1 o Sample-2

0.15 0.15

°'° 0.10
Ihl m o.2 "
0.05 0.05

0 , i -- 0 0 ~ '

0 0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 1
Conversion Conversion Convemion

Measured Activation Energies

, Sample-1 , Sample-2 = Sample-1 n Sample-2

60 60
"6
", ,, m, ''dpm"
•
° ~ [] ° ,.0._-"
50 50
• • mm

UJ
40 J 40 J

0 0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 1
Conversion Conversion Convemion

C a l c u l a t e d Y i e l d C u r v e s for Total H y d r o c a r b o n G e n e r a t i o n

Sample-1 Sample-2 Sample- 1 Sample-2

1. I I

~P
>
c

0
0
0,5/ 0.5 //
i i ,

0.4 0.6 0.8 1 1.2 1.4 1.6

, , 0

0.4 0.6 0.8 1

~

1.2 1.4 1.6

0 /,//

0.4 0.6 0.8 1 1.2 1.4 1.6

Estimated vitrinite reflectance Estimated vitrinite reflectance Estimated vitrinite reflectance
Fig. 7. As Fig. 6 but for Type II source rocks.

beginning at VREs of 0.5-0.6) and continue to the Type II source rocks, the last 20% or so of generation
same maturities. Indeed, the kinetics of mature Type occurs very slowly and is not completed in a reason-
II source rocks approach those of Type I. The more able time at the isothermal temperatures used.
rapid initial generation appears to be related to the Apparent reaction orders are measured in the range
higher initial organic sulphur content of their kero- 3.0-4.4. Activation energies increase rapidly to
gens. Monterey-l, which has the highest sulphur values around 53-54 kcal/mol, and to 54-58 kcal/mol
content of all samples measured, begins to generate at high conversions. The higher initial reaction rates
at VREs as low as 0.4. The early generated products (much higher than those of Type I kerogens) cannot
correspondingly have high S/C ratios. It should be be attributed to organic sulphur, which is low in all
re-emphasised that these open system experiments these source rocks. Other relatively weak bonds must
are not expected to predict the generation of high- be invoked, possibly oxygen-containing linkages.
molecular-weight hydrocarbons (C4o+). In view of the difficulty of exhaustively extracting
bitumen from coals, it is also possible that part of the
Type III initially high rate is from residual bitumen that has
Type III coals show a wide range of reaction rates been liberated thermally.
as a function of conversion (Fig. 8). Although reac- In naturally matured coals from the Carbonifer-
tion rates at low conversions may be as high as for ous of the Netherlands (VR 0.95-1.0%) activation
56 U . C . KLOMP and P. A. WRIGHT

Source Rock Transformation rate at 340°C

Sarawak Indonesian Netherlands

• Sample- 1 , Sarnple-3 X Sample-1 v Sample-3

o Sample-2 o Sample-4 O Sample-2
0.10 " 0.10 / v" 0.10
DQ

[3

0.05 0.05 X 'gQ. 0.05

/ x ,~

=I=~L
0 r o
0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
Conversion Conversion Convemion

Measured Activation Energies

• Sample- 1 • Sample-3 x Sample-1 v Sample-3
n Sample-2 o Sample-4 o Sample-2
60 6O 60
"6 n un -,

50 50 x ~" 5O

LU

40 . . . . 40 , , 40
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
Conversion Conversion Conversion

Calculated Yield Curves for Total Hydrocarbon Generation

Sarnple-1 Sample-3 Sample-1 Sample-3
Sarnple-2 Sample-4 Sample-2

J
8
E¢1
0.5
O
o

0 r J J i q r T i , 0 J ~ v ~ q

0.4 0.6 0.8 1 1.2 1.4 1.6 0.4 0.6 0.8 1 1.2 1.4 1.6 0.4 0.6 0.8 1 1.2 1.4 1.6
Estimated vitrinite reflectance Estimated vitrinite reflectance Estimated vi~'inite reflectance
Fig. 8. As Figs 6 and 7, but for Type III coals.

energies for generation are in the range
53-58 kcal/mol once unextracted bitumen has been
removed. Primary generation of hydrocarbons from
coals is predicted to begin at VREs of 0.6-0.7 and
continue gradually over a very wide range of matu-
rity, certainly until the VRE exceeds 1.6.
No source rocks containing dispersed Type III
kerogen are included in this report, inasmuch as they
are the subject of ongoing research.
COMPARISON OF PREDICTED WITH
NATURAL DATA
The conversions calculated from laboratory-de-
rived kinetic parameters can be compared with natu-
ral data to check whether they extrapolate to
geological conditions. The most direct manner of
obtaining conversion data from natural samples is
from the pyrolysis of source rocks of different natural
maturity. An initial hydrocarbon yield per unit car-
bon can be calculated for immature samples by
plotting their pyrolysis yield against their total
organic carbon. As the source rock is converted
naturally, the hydrocarbon yield per unit organic
carbon will be reduced if the generated oil has a
higher H/C ratio than the immature source rock. The
conversion can then be calculated by an equation of
the form (Pelet, 1985).
Conversion = {HI(he). [HI(imm) - HI(mat)]} (6)
{HI(imm). [HI(he) - HI(mat)]} '
where HI(he) is the mass of hydrocarbons gener-
ated p e r u n i t m a s s o f c a r b o n in the p r o d u c t a n d
 Measurement of the kinetic parameters of hydrocarbon generation 57

• USA • Gabon 0.04

~, Thailand-1 o Torbanite 340°0
0.15
J~
Type I
O.lO
E 0.02

~ 0,~ • ll

O.O0 . t ~ - ' : ' - . . . . 3"-'- . . . . . . . . : ..........

0.0 0.2 0.4 0.6 0.00
0.2 04 0.6 08 1

'Conversion'
• Ki_m__m;l__. • Monterey,-1.. 60
a Hanifa o Mon__~rey-2

.O
0.15
L. Type I1 .~
J O
• • • illl•ll
.~_ o.lo / 50
E
.9 " "'-- LU
~ 0.05

40
0.00 i i 0:2 0:4 016 o18
0.0 0.2 0.4 0.6
'Conversion'
Fig. 10. The kinetic parameters of the isothermal reaction
rate at 340°C and the activation energy plotted against
• Netherlands conversion from a mature sample of the Hanifa Fm., Qatar
[] Sarawak 1 (VRE =0.78). The "conversion" fraction relates to the
0.15 laboratory conversion of the mature source rock and does
0
not take into account the natural conversion (estimated at
Type III 6o%).
o 0.10
E were calculated using modified Lopatin calculations
.9
on the burial histories and the yield curve was
o 0.05 calculated using a heating rate appropriate to the
regional geological environment: the data agree
0.00 within experimental and geological accuracy. Direct
oo o12 0:4 08 comparison with our laboratory measurements
Fraction of total carbon Hanifa Fro. O Natural data
Fig. 9. The atomic S/C ratio of pyrolysates evolved upon
non-isothermal pyrolysis (200°C/min) of selected isolated
kerogens and coals. In the method, the pyrolysate is immedi-
ately burnt and the oxides measured by mass spectroscopy
(see text for details).

HI(imm) and HI(mat) are "corrected" hydrogen

~
O
0 . 5

indices of immature and mature source rocks (slopes o

of plots of milligrammes of pyrolysate yield vs
grammes of organic carbon).
This method is prone to error, however, particu-
0
larly at low conversions, where the generated prod- 0.4 0.6 0.8 1 .2
ucts and the kerogens will have similar compositions Modified Lopatin VR/E
and there may be local variations in the original
TOybServedan.d.predicted ke.rogen conversion
hydrocarbon potential due to facies differences. Nev- pe II - H a n i t a s o u r c e rOCK
ertheless, it provides the most direct test of predicted Fig, I l, Estimates of the conversion of naturally matured
conversion and in cases where good data is available Hanifa Fm. source rocks, Qatar, as calculated from Rock
from mature source rocks it can be reliably applied. Eval data assuming the generation of hydrocarbons with a
Figure 11 compares estimates of the natural conver- bulk H/C ratio of 2, as described in the text. The curve is
the generation calculated by numerical integration of kinetic
sion of source rocks of the Type II Hanifa formation data extrapolated using an estimate of the regional heating
of Qatar with a yield curve calculated from kinetic rate for this source rock. (The conversion/VRE plot is
parameters. The maturities of individual samples almost independent of the heating rate.)
58
would predict sulphur-rich oils to be generated below
0.7-0.8 VRE, above which oils poorer in sulphur
would be generated by a near first-order process.
DISCUSSION
The kinetic method outlined above gives an
isothermal rate of conversion and activation energies
measured to a precision of 1-2 kcal/mol. If the data
are compared to those obtained non-isothermally
(Campbell et al., 1978; Burnham et al., 1987; Ungerer
and Pelet, 1987), then--for the Green River shales at
least--the activation energies measured by our
method are closer to those derived by the first two
groups of authors (52.4 and 51.0 kcal/mol) than the
last group (56 kcal/mol). For a range of source rocks,
the activation energies are in the range measured
elsewhere from the fitting of non-isothermal data
• Thispaper
o.o4 I
i 0,02
o:2 0:4 0:8
Conversion
(a) Source rock transformation at 340°C
USA Green River Fm.
• This paper (Hanifa)
0.10
1 bonds in particular has been discussed in the litera-
%
%.
c0 0.05 %.
%
0.00 , , "It__
o o'.a o'.4 0.6
Conversion
(b) Source rock transformation at 340°C
Marine source rocks
Fig. 12. Comparison of the isothermal rate data measured
in these experiments with the values calculated using kinetic
parameters obtained by non-isothermal pyrolysis from (a)
the Green River shale [E = 52.4kcal/mol, A =2.8E13/s
(Campbell et al., 1978)] and (b) from a marine shale
(distribution of E, 5% with 47kcal/mol, 20% with
48 keal/mol, 50% with 49 kcal/mol, 20% with 50 kcal/mol
and 5% with 51 kcal/mol, A -5.1E12/s (Burnham A. K.,
personal communication 1989)].
U.C. KLOMPand P. A. WRIGHT
(Tissot et al., 1987; Burnham et al., 1987). If the
isothermal rate curves are compared with those calcu-
lated using kinetic parameters from non-isothermal
heating [Figs 12(a, b) (Burnham A. K. personal com-
munication 1989)] there is good agreement for the
Green River shale and reasonable agreement for a
marine shale, bearing in mind the observed variation
in such samples. For the latter sample, the curvature
in the rate vs conversion plot from Burnham's data
comes from a distribution of activation energies
from 47 to 51 kcal/mol. Similarly, the lower than
first-order behaviour of torbanite and other Type I
samples has been observed previously and attributed
to an induction period in which consecutive bond-
breaking events are required to liberate hydrocarbons
(Bar et al., 1988).
The method outlined in this paper has the
advantage of making more direct measurement of
activation energies compared to non-isothermal
[] Campbellat al methods, which assume that conversion takes place
through parallel first-order reactions with identical
pre-exponential factors. In common with other open
system experiments, our method gives no information
on the generation of high-molecular-weight products
and the extrapolation of the rate data to geological
conditions breaks down if the mechanism in the two
cases is not the same (Burnham et al., 1989).
Although the method allows the determination of
the kinetics of individual source rocks, the predicted
yield curves group roughly according to classical
kerogen types--terrestrial lacustrine/algal (Type I),
0:8 terrestrial landplant (Type III) and marine (Type II).
High concentrations of sulphur in Type II kerogens
promote more rapid conversion initially. In the later
stages of conversion, however, the generation kinetics
are close to those of Type I rocks (first order), with
Burnham,1988 products poorer in sulphur. As the method is only
applicable to hydrocarbons that are volatile below
350°C, heavy oil generation cannot be modelled
adequately.
The role of weak bonds in general and sulphur
ture (Jones, 1984; Sinninghe Damst6 et aL, 1989).
High-sulphur kerogens at low maturity are found to
contain considerable quantities of bitumen with large
proportions of asphaltenes. Although much of this
may be a product of diagenesis and may never have
been incorporated into the larger kerogen molecules,
o.5 the remainder is probably liberated by the cleavage of
weak bonds. If there are insufficient weak links to
break up the kerogen into products with low enough
molecular weight to be volatilised in our experiments,
the released pyrolysates will be generated by acti-
vation energies of C - - C bond breaking. The re-
duction in connectivity following weak-link breakage
may only result in an increase in the pre-exponential
reaction factor and a change in the apparent order.
Models for the decomposition of polymers by a
free-radical chain mechanism involving the steps of
initiation, propagation and termination that assume
 Measurement of the kinetic parameters of hydrocarbon generation 59

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