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

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

49
50 U.C.KLoMPandP.A.WRIGHT
fraction of the total potential hydrocarbon gener- 25.
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 lO
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
-i o 60 i~ 200 2~o
Time at 340=0 (h)
source rock is heated at a constant temperature (Tm~t)
between 300-350°C. The rate may then be expressed Fig. 1. The FID signal vs the time of isothermal maturation
at 340~C for a just mature Kimmeridge source rock. The
as an empirical function of the conversion: area A 2 (which equals the time integral of the FID signal
between the start of the experiment and time t) is pro-
Rate(Treat, x) = krm.,(x) "frm.,(X). (2) portional to the amount of hydrocarbons produced up to
The activation energy is then measured by follow- time t. The constant area A~ + A2is proportional to the total
amount of hydrocarbons produced. Therefore, at time t the
ing the reaction rate as the temperature is increased conversion is defined as the ratio A2/Am+A2. Conse-
in steps of 10°C. Relating the rate at each tempera- quently, the rate of conversion corresponds to the derivative
ture to that at a reference temperature (Trot) at the of the ratio with respect to time, which equals the FID signal
same conversion, divided by Aj + A 2.

Rate(T, x) = Rate(Tref, x). exp[-E(x)/RT]

to 0.80. For the just mature Kimmeridge source rock
x exp[E(x)/RT~f], (3) this gave a value for n of 1.56. The apparent reaction
order measured in this way, which will depend on the
a measurement of the activation energy can be made
temperature at which it is determined if the activation
by regression of the equation
energy varies as a function of conversion, gives
Rate(T, x) = Rate(Tr~f, x) no information on the reaction order of individual
reactions which may be occurring with a range of
xexp{-[E(x)/R].(l/T- 1/T~f)} (4)
different kinetic parameters; it cannot be used in
or, more correctly, by a linear regression of direct extrapolation to geological temperatures.
To determine the activation energy of generation,
In(Rate(T, x )/Rate( Trcf, x ))
the rate must be measured as a function of tempera-
=[E(x)/RT,~I-[E(x)/R]. I/T. (4a) ture without changing the degree of conversion. To
this end, at different states in the isothermal heating
An example of the method is given using a Kim- (and therefore at different conversions which may
meridge source rock of natural maturity estimated
later be calculated from the complete signal vs time
at 0.64% VRE (vitrinite reflectance equivalent). plot) the temperature is rapidly lowered well below
Figure I, shows the signal plotted vs time for the just
the isothermal maturation temperature and then
mature source rock heated at 340°C, which can then raised stepwise, allowing enough time for a measure-
be converted into a plot of a normalised rate vs
ment of the rate at each temperature (Fig. 3). The
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 0.05
apparent order of the reaction can be made from the q
isothermal rate vs conversion data. A rearranged "7
0.04
form of equation (1), C
0
•~ 0.03
In(Rate) = In k + n ln[l - x], (5) 0

0
gives a plot whose slope gives the apparent reaction I 0.02, Oo O
"6
order. In fact, the plots of these variables often show Oo
curvature, particularly at low and high conversions, ~0.01
indicating that the apparent order, the activation
energy, the pre-exponential factor or combinations of 0,00 , o ~
all three are dependent on the conversion. To enable 0 012 014 0.6 0.8 1
the rate's decrease with conversion to be parameter- Conversion at 340°C
ised, the apparent order was calculated by linear Fig. 2. The normalised rate of conversion (per hour) vs the
regression of equation (5) for conversions from 0.20 conversion as calculated from the data of Fig. 1.
 Measurement of the kinetic parameters of hydrocarbon generation 51

55.
[] []
v
• []
• •
g
8 []

• Tm=310°C
[] Tm=340°C

o o12 014 o:6 o'.e

•4 ~ ltme Conversion
Fig. 3. The FID signal obtained while measuring the effect Fig. 5. The activation energy, determined during different
of temperature on the rate of hydrocarbon generation for isothermal heating experiments with maturation tempera-
the Kimmeridge source rock. This experiment consists of tures of 310 and 340°C, plotted as a function of conversion.
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 Once both the rate (Trot) and the activation energy
each cycle. At the start of each step, the temperature is
increased rapidly by about 10°C. The numbers on top of the
E have been determined experimentally as a function
curves denote the final temperature for each step. Above of conversion, the source rock conversion can be
291.8°C the FID signal is attenuated by a factor of 2 with calculated at any stage during source rock burial by
respect to the preceding step. means of numerical integration when the temperature
history is known. An estimate of the VRE maturity
time steps and temperatures are chosen so that the of the source rock can also be made using a modifi-
change in conversion during the determination of an cation of the Lopatin method, where, in place of the
activation energy is very small, less than around 3% factor 2 for the rate increase per 10°C, a factor was
at conversions greater than around 10%. (It is used which improved the fit of a natural data base of
difficult to measure activation energies at very low vitrinite measurements and related burial histories
conversions because of the very high rates of conver- when calibrated on a single VR vs TTI line. Plotting
sion. In addition to conversion, these high rates may calculated conversion of the kerogens against esti-
reflect desorption of unextracted bitumen or tightly- mated VR allows source rocks with different geologi-
bound solvent). To a good approximation, then, the cal histories to be compared. It was felt that for the
activation energy is determined at a single conver- purposes of this paper the VRE maturity was a
sion. The activation energy is, in practice, determined convenient and interesting axis for the comparison of
from an Arrhenius plot (Fig. 4) that is the linear the different source rock types, notwithstanding the
regression of equation (4a). By repeating this tem- additional errors that may be included by modelling
perature program at different stages in the matu- the VR at the same time as the conversion.
ration, the activation energy is determined as a The key assumptions made by this method are that
function of conversion (Fig. 5). 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
Legend
cracking process and are not apparent values result-
10 _ • 8.3 h 340"C
ing from the superposition of a wide variety of
[] 28.3 h 340"C
reactions of different activation energies (which might
t~ --,,!, I. se.s h 3~0C
also have different pre-exponential factors). If, say,
o ~ 0 135.3 h 340"C
reactions with activation energies of 40-60 kcal/mol
6 o : ~ -~.Ok~L~mo, were responsible for the conversion, then upon arti-
In
ficial maturation at different isothermal tempera-
v 0 • []
c 4
o • []
tures, lower temperatures would initially favour
0 • -'~ 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 1.~5 1.~o i.~s 1.~o 1.~ 1.6o
very wide spread of activation energies were respon-
lOOO/1"
sible for hydrocarbon generation, then the lower
Fig. 4. Arrhenius plots of the logarithm of the rate of temperatures of natural maturation would greatly
hydrocarbon generation (FID signal ) at temperature T vs
the reciprocal absolute temperature. The activation energy favour the reactions of low activation energy and
is thus determined at four different stages of isothermal reactions of much higher activation energy would be
maturation. 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- expelled at the higher temperature to be removed).
served in the later stages of artificial maturation of For the temperature increase, steps of 40 min were
immature source rocks. usually enough for the signal to reach a steady value.
(Because of the relatively slow rates of conversion the
EXPERIMENTAL METHOD generation rate at each temperature is approximately
constant.) The highest temperature of the stepwise
Source rock samples are finely ground to a grain increase is arranged to be the maturation tempera-
size of no larger than about 150/tm and placed for ture, so that after the stepping the isothermal matu-
1 week in a Sohxlet apparatus, where bitumen is ration is continued. The time spent in the activation
extracted with chloroform/methanol. The samples energy determination is converted to an effective
are then dried at 100°C under 200mbar nitrogen. maturation time at the isothermal temperature by
50-200 mg of the source rock are put in a stainless- assuming a doubling of rate with each 10°C rise in
steel sample chamber (40mm long with i.d.= temperature and thus dividing the actual time spent
2.7 ram) and heated overnight in a modified gas in each step by a factor 2(rm'- ~/:0, where Tm,t is the
chromatography oven in 10 cma/min of flowing nitro- isothermal maturation temperature and T is the
gen at 150-200°C to remove the remaining solvent. temperature of the step.
Pyrolysate that is volatile at the experimental tem- At the maturation temperatures usually adopted,
peratures (260-360°C) is measured by a flame ion- an experiment takes from 2 to 3 weeks. Temperature
isation detector (FID). By switching the flow of programming and data collection are fully auto-
carrier gas through the sample chamber away from mated. The sample yield is measured before and after
the FID detector, a background signal can also be heating to determine the final conversion.
measured. The temperature remains stable to 0.3°C, It should be noted that the experimental method
as measured by PT100 resistance thermometers in- limits the kinetic analysis to products that are volatile
serted into each sample chamber less than 1 cm away at temperatures between 260-360°C. In practice, this
from the sample. Measured temperatures at different corresponds to compounds with boiling points as
positions within the oven may vary by up to 2°C, high as those of normal C30-C40 alkanes. For less
but remain constant at each position. The PTI00 volatile hydrocarbons the measured kinetics may be
thermometers are used as supplied (random in-house rate-limited by evaporation. Our measured kinetics
calibration up to 200°C with a quartz reference will therefore apply to the generation of medium to
thermometer showed that the PTI00s gave tempera- high API gravity oils rather than to heavy oils.
tures within 0.3°C of the quartz thermometer). Kinetic measurements have been performed on a
The temperature is increased in steps to the isother- variety of immature source rocks of different kerogen
mal maturation temperature, and this initial signal/ types, for which standard pyrolysis and maceral data
time history is later converted to expected signal and were available (Tables 1 and 2). For comparison, the
time at the maturation temperature. In the activation kinetics of some naturally mature source rocks have
energy determination, the temperature is first reduced also been determined. In addition, the composition
and the sample is given 2 h to reach a steady state of the pyrolysate was determined by an elemental
(allowing all the volatile bitumen generated and not 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 algal remains, whereas the torbanite from Australia
method of van Leuven et al. (1988). Kerogen isolates is made up largely of recognisable Botryococcus
and coals were analysed using a heating rate of algae.
200°C/rain up to 1000°C, followed by combustion. A first-order reaction with a single activation
During pyrolysis, two sulphur peaks are observed; energy would appear as a straight line on the rate
the first comes from organic sulphur, the second from vs conversion plots. The algal S.O.M. source rocks
pyrite decomposition. Carbon, hydrogen and sulphur (see Fig. 6) in fact, approximate this behaviour.
atomic ratios are given in Table 2, split up into total This near first-order behaviour [n (apparent) = 1.3 to
and pyrolysate compositions. 1.6] may be explained by the kerogens' chemical
homogeneity and their low sulphur content. At
very low conversions they have higher reaction
RESULTS rates, though, since residual solvent or bitumen
is removed particularly in the first few percent of
The results for each source rock's reaction kinetics conversion.
are summarised in plots of the isothermal generation The highly structured, algal torbanite sample
rate and the activation energy, both measured as a converts much more slowly than the other Type I
function of conversion (Figs 6-8). Although iso- samples. The isothermal rate at lower conversions is
thermal maturation took place at temperatures be- lower than a first-order model would predict--the
tween 310-360°C, according to the thermal reactivity apparent reaction order is 0.71.
of the source rock, all rate data are converted to a Activation energies for generation from the Type I
standard temperature (340°C) to facilitate compari- source rocks vary from 49 to 55 kcal/mol; most of the
son. Apparent reaction orders were calculated for generation occurs with values at the lower end of this
rate data at conversions between 0.2-0.8. range. Average values from the torbanite are at the
Using a numerical integration method, the con- upper end of this range (52.5-55 kcal/mol). These
version curves of each kerogen type were calculated measured values are in reasonable agreement with
and plotted against an estimate of the VR assuming those measured elsewhere (Campbell et aL, 1978;
a heating rate of 3.3°C/my. The VR rather than Ungerer and Pelet, 1987).
temperature was plotted on the x-axis to enable the In general, the pyrolysates of Type I source rocks
comparison of source rocks with different burial were very low in sulphur (total S/C < 0.02; see
histories. Table 2 and Fig. 9).
The atomic sulphur/carbon ratios of pyrolysates as Type I source rocks are predicted to generate a
a function of conversion determined by pyrolysis-- sulphur-poor product over a narrow maturity inter-
combustion-mass spectrometry are displayed in val, which for the kerogens containing poorly struc-
Fig. 9. tured organic matter is mainly from 0.75 to 1.0 VRE,
with a peak generation rate, assuming linear heating,
Type I
at 0.85-0.9VRE. The torbanite, which generates
The source rocks from the U.S.A., Thailand and more slowly than the other, less-structured algal
Gabon are composed predominantly of structureless source rocks, is predicted to generate at a higher
algal organic matter (algal S.O.M.), with recognisable 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 content. The S/C ratio is seen to fall off rapidly with
made up of bacterially transformed S.O.M., a wider conversion (see Fig. 9).
range of kinetic behaviour is observed than for the A naturally matured and partly converted Hanifa
Type I S.O.M. samples (Fig. 7). In particular, the source rock (VRE=0.78) was also examined
Monterey samples have higher initial rates of gener- (Fig. 10). The natural conversion of this sample is
ation. The marked curvature of the isothermal rate estimated at 60% from Rock Eval measurements (see
plots indicate a higher apparent reaction order, which below). The reduction in the reaction rates and
is between 1.9-2.4 for all except the Monterey-1 apparent order as well as the high activation energy
sample, for which it is 3.4. The activation energies (around 53 kcal/mol) is consistent with a lower
measured vary from 46 to 55 kcal/mol, usually show- proportion of weak bonds at high maturities.
ing a gradual increase with conversion. All source The Type II source rocks start to generate
rocks show higher reaction rates than those of Type I, 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 obtaining conversion data from natural samples is
53-58 kcal/mol once unextracted bitumen has been from the pyrolysis of source rocks of different natural
removed. Primary generation of hydrocarbons from maturity. An initial hydrocarbon yield per unit car-
coals is predicted to begin at VREs of 0.6-0.7 and bon can be calculated for immature samples by
continue gradually over a very wide range of matu- plotting their pyrolysis yield against their total
rity, certainly until the VRE exceeds 1.6. organic carbon. As the source rock is converted
No source rocks containing dispersed Type III naturally, the hydrocarbon yield per unit organic
kerogen are included in this report, inasmuch as they carbon will be reduced if the generated oil has a
are the subject of ongoing research. higher H/C ratio than the immature source rock. The
conversion can then be calculated by an equation of
COMPARISON OF PREDICTED WITH the form (Pelet, 1985).
NATURAL DATA
Conversion = {HI(he). [HI(imm) - HI(mat)]} (6)
The conversions calculated from laboratory-de- {HI(imm). [HI(he) - HI(mat)]} '
rived kinetic parameters can be compared with natu-
ral data to check whether they extrapolate to where HI(he) is the mass of hydrocarbons gener-
geological conditions. The most direct manner of 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 U.C. KLOMPand P. A. WRIGHT

would predict sulphur-rich oils to be generated below (Tissot et al., 1987; Burnham et al., 1987). If the
0.7-0.8 VRE, above which oils poorer in sulphur isothermal rate curves are compared with those calcu-
would be generated by a near first-order process. 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
DISCUSSION
Green River shale and reasonable agreement for a
The kinetic method outlined above gives an marine shale, bearing in mind the observed variation
isothermal rate of conversion and activation energies in such samples. For the latter sample, the curvature
measured to a precision of 1-2 kcal/mol. If the data in the rate vs conversion plot from Burnham's data
are compared to those obtained non-isothermally comes from a distribution of activation energies
(Campbell et al., 1978; Burnham et al., 1987; Ungerer from 47 to 51 kcal/mol. Similarly, the lower than
and Pelet, 1987), then--for the Green River shales at first-order behaviour of torbanite and other Type I
least--the activation energies measured by our samples has been observed previously and attributed
method are closer to those derived by the first two to an induction period in which consecutive bond-
groups of authors (52.4 and 51.0 kcal/mol) than the breaking events are required to liberate hydrocarbons
last group (56 kcal/mol). For a range of source rocks, (Bar et al., 1988).
the activation energies are in the range measured The method outlined in this paper has the
elsewhere from the fitting of non-isothermal data advantage of making more direct measurement of
activation energies compared to non-isothermal
• Thispaper [] Campbellat al methods, which assume that conversion takes place
through parallel first-order reactions with identical
o.o4 I 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
i 0,02 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),
o:2 0:4 0:8 0:8 terrestrial landplant (Type III) and marine (Type II).
Conversion High concentrations of sulphur in Type II kerogens
(a) Source rock transformation at 340°C promote more rapid conversion initially. In the later
USA Green River Fm. stages of conversion, however, the generation kinetics
are close to those of Type I rocks (first order), with
• This paper (Hanifa) Burnham,1988 products poorer in sulphur. As the method is only
0.10 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
1 bonds in particular has been discussed in the litera-
%
%.
c0 0.05 %. 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
0.00 , , "It__ been incorporated into the larger kerogen molecules,
o o'.a o'.4 0.6 o.5 the remainder is probably liberated by the cleavage of
Conversion weak bonds. If there are insufficient weak links to
(b) Source rock transformation at 340°C break up the kerogen into products with low enough
Marine source rocks molecular weight to be volatilised in our experiments,
the released pyrolysates will be generated by acti-
Fig. 12. Comparison of the isothermal rate data measured
in these experiments with the values calculated using kinetic vation energies of C - - C bond breaking. The re-
parameters obtained by non-isothermal pyrolysis from (a) duction in connectivity following weak-link breakage
the Green River shale [E = 52.4kcal/mol, A =2.8E13/s may only result in an increase in the pre-exponential
(Campbell et al., 1978)] and (b) from a marine shale reaction factor and a change in the apparent order.
(distribution of E, 5% with 47kcal/mol, 20% with
48 keal/mol, 50% with 49 kcal/mol, 20% with 50 kcal/mol Models for the decomposition of polymers by a
and 5% with 51 kcal/mol, A -5.1E12/s (Burnham A. K., free-radical chain mechanism involving the steps of
personal communication 1989)]. initiation, propagation and termination that assume
 Measurement of the kinetic parameters of hydrocarbon generation 59

the products are generated mostly in the propagation REFERENCES

step and adopt the steady-state approximation with
Anthony D. B., Howard J. B., Hottel H. C. and Meissner
respect to radical concentrations (Rice and Herzfeld, H. P. (1975) Rapid devolatilization of pulverized coal.
1934; Frost and Pearson, 1963) give overall activation In Proc. 15th Int. Symp. on Combustion, p. 1303. The
energies of the general form Combustion Institute, Pittsburgh.
Bar H., Ikan R. and Aizenshtat Z. (1988) Fossil fuels and
Eov,ra,, = Ep + l/2(Ei - E0. (7) synthetic polymers: isothermal pyrolysis kinetics as indi-
cation of structural resemblance.J. Anal. Appl. Pyrol. 14,
Assuming the bond-breaking energies (Ei) lie 73-79.
between 60 kcal/mol for C--S and S--S bonds and Burnham A. K. and Braun R. L. (1985) General model of
80 kcal/mol for C - - C bonds (Chemical Rubber Co., oil shale pyrolysis. In Situ 9, 1-23.
Burnham A. K., Braun R. L., Gregg H. R. and Samoun
1983), and relying on literature values for energies of A. M. (1987) Comparison of methods for measuring
propagation Ep (hydrogen abstraction, 20 kcal/mol) kerogen pyrolysis rates and fitting kinetic parameters.
and termination Et (radical diffusion, 10 kcal/mol) J. Energy Fuels 1, 452-458.
(e.g. Stivala et al., 1983), then the range of energies Burnham A. K., Braun R. L. and Samoun A. M. (1988)
will be approx. 45-55 kcal/mol. The observed range Further comparison of methods for measuring kerogen
pyrolysis rates and fitting kinetic parameters. In Advances
is 46-55 kcal/mol for Types I and II source rocks, in Organic Geochemistry 1987 (Edited by Mattav¢lli L.
with slightly higher values for coal pyrolysis. and Novelli L.). Org. Geochem. 13, 839-845. Pergamon
Although such agreement is probably somewhat Press, Oxford.
fortuitous, it does explain the magnitude of the Burnham A. K., Oh M. S., Crawford R. W. and Samoun
A. M. (1989) Pyrolysis of Argonne premium coals:
activation energy. activation energy distributions and related chemistry.
It should be emphasised that the results presented J. Energy Fuels 3, 42-55.
here relate to total hydrocarbon generation from Campbell J. H., Koskinas G. J. and Stout N. D. (1978)
a nearly open system, at least for those reaction Kinetics of oil generation from Colorado oil shale. Fuel
products that are volatile at the experimental tem- 57, 372-376.
Chemical Rubber Co. (1982/83) Handbook of Chemistry and
peratures. To investigate the effect of retention and Physics, 63rd edn (Edited by West R. C.). CRC Press,
secondary cracking on the yield curves in nature, Boca Raton, FL.
the rate of primary migration must be known Friedman H. L. (1963) Kinetics of thermal degradation
(e.g. Stainforth and Reinders, 1990). of char-forming plastics from thermogravimetry. Appli-
cation to a phenolic plastic. J. Polym. Sci. Part C 6,
183-195.
CONCLUSIONS Frost A. A. and Pearson R. G. (1963) Kinetics and
Mechanism, Chap. 10. Wiley, New York.
1. The method described here enables reaction rates Jones R. W. (1984) Comparison of carbonate and shale
source rocks. In Petroleum Geology and Source Rock
and activation energies to be measured separately Potential of Carbonate Rocks (Edited by Palacas J. G.),
as functions of conversion for individual source pp. 163-180. AAPG Stud. Geol. 18, Am. Assoc. Pet.
rocks. The measured activation energies for hydro- Geol., Tulsa, OK.
carbon generation lie in the range 46-58 kcal/mol, Juntgen H. and Heek K. H. van (1979) An update of
German non-isothermal coal pyrolysis work. Fuel
the bulk of them being between 49-55 kcal/mol. Process. Technol. 2, 261-293.
Naturally matured samples have activation ener- Leuven H. C. E. van, Grondelle M. C. van, Meruma A. J.
gies at the top of these ranges. and Vos L. L. de (1988) A multielement evolved gas
2. Extrapolation of these kinetic parameters to analysis technique: design, performance and industrial
natural temperatures is possible by a numerical applications. In Compositional Analysis by Thermo-
gravimetry (Edited by Earnest C. M.). A S T M STP 997,
integration method. The source rocks examined 170-174. ASTM, Philadelphia, PA.
vary in behaviour broadly according to kerogen Lewan M. D. (1985) Evaluation of petroleum generation by
type, Type I generating over a relatively narrow hydrous pyrolysis experimentation. Philos. Trans. R. Soc.
range and Type III over a wide range. Type II London A315, 123-134.
Pelet R. (1985) I~valuationquantitative des produits form,s
source rocks show intermediate behaviour. Gener- lors de l'rvolution g~ochimiquede la mati~re organique.
ation of heavy crudes cannot be modelled by this Rev. Inst. Ft. Pbt. 40, 551-562.
method. Quigley T. M. and MackenzieA. S. (1988) The temperatures
3. The predicted kerogen conversions are consistent of oil and gas formation in the subsurface. Nature
with available natural data on the homogenous (London) 333, 549-552.
Rice F. O. and Herzfeld K. F. (1934) The thermal decompo-
Type II Hanifa Fm. source rock. sition of organic compounds from the standpoint of free
radicals. VI. The mechanism of some chain reactions.
Acknowledgements--We thank Maarten Muller von Czer- J. Am. Chem. Soc. 56, 284.
nicki for his technical assistance throughout the experiments Sinninghe Damst~ J. S., Egiinton T. I., Leeuw J. W. de and
and Arie Meruma of the Koninklijke Shell Laboratorium in Schenk P. A. (1989) Organic sulphur in macromolecular
Amsterdam for coordinating the temperature-programmed sedimentary organic matter: I. Structure and origin of
elemental analyses. We also thank the Shell Internationale sulphur-containing moieties in kerogen, asphaltenes and
Petroleum Maatschappij B. V. and the Shell Internationale coal as revealed by flash pyrolysis. Geochim. Cosmochim.
Research Maatschappij B. V. for permission to publish this Acta 53, 873-889.
work. The careful reviewingof Alan Burnham is also greatly Stainforth J. G. and Reinders J. E. A. (1990) Primary
appreciated. migration of hydrocarbons by diffusion through organic
60 U.C. KLOMPand P. A. WRIGHT

matter networks. In Advances in Organic Geochemistry Tissot B. P. and Espitali6 J. (1975) L'6volution thermique
1989(Edited by Durand B. and Behar F.). Org. Geochem. de la mati~re organique des s~iments: applications
16, 61-74. Pergamon Press, Oxford. d'une simulation math~matique. Rec. Inst. Ft. P~t. 30,
Stivala S. S., Kimura J. and Reich L. (1983) The kinetics of 743-777.
degradation reactions. In Degradation and Stabilization of Tissot B. P., Pelet R. and Ungerer P. (1987) Thermal history
Polymers, Vol. 1 (Edited by Jellinek H. H. G.), Chap. 1, of sedimentary basins, maturation indices and kinetics of
pp. 1-65. Elsevier, Amsterdam. oil and gas generation. Bull. ,4m. Assoc. Pet. Geol. 71,
Tissot B. P. (1969) Premi6res donn6es sur les m6canisms et 1445-1466.
la cin6tique de la formation du p6trole dans les s6diments: Ungerer P. and Pelet R. (1987) Extrapolation of the kinetics
simulation d'un sch6ma r6actionnel sur ordinateur. Rev. of oil and gas formation from laboratory experiments to
Inst. Fr. Pdt. 24, 470-501. sedimentary basins. Nature (London) 327, 52-54.