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UCRL-JC-H7269
PREPRINT
Comparison of Kinetic Analysis ofSource Rocks and Kerogen Concentrates
John G. ReynoldsAlan K. Burnham
HO
Zbf-
This paper was prepared for submittal toOrganic Geochemistry
May 10,1994
Thisisapreprintofapaper intended for publication in a journal or proceedings. Since
changes may be made before publication, this preprint is made available with the
understanding mat it will not be cited or reproduced without the pemtiMion of the
author.
OANCOPY
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DISCLAIMER
Thh document was prepared as an account of work sponsored by aa ageacy of the
United Stales Government. Neither the United States Gonenuneot nor the University
of California nor any of their employe**, nukes aay warranty, express or Imatttd, or
assumes my legal liability or responsibility for the accuracy, completeness, or aaefmV
aess of aay information, apparatus, product, or process disclosed, or it pre wars that
its use would not infringe privately owned rights. Reference herein to aay specific
commercial products, process, or service by trade name, trademark, manufacturer, or
otherwise, does not necessarily constitute or imply its endorsement, recomiattmafiott,
or favoring by the United States Government or the University of California. The
views and opinions of authors expressed herein do not necessarily state or reflect
those of the United States Government or the University of California, and shall not
be used for advertising or product endorsement purposes.
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*
COMPARISON OF KINETIC ANALYSIS OF
SOURCE ROCKS AND KEROGEN CONCENTRATES
John G. Reynolds and Alan K. Burnham
University of California
Lawrence Livermore National Laboratory
Livermore, CA 94551
ABSTRACT
Shales and kerogen concentr ates from th e Green River, Rundel,
Ohio, Kimmeridge, and Phosphoria formations were examined byPyromat II micropyrolysis and kinetic parameters were
determined by the shif t - in-T m a x , d i s c r e t e d i s t r i b u t i o n ,
modified Friedman, and modified Coats-Redfern methods.
Overall, the shales and corresponding kerogens exhibited very
simi lar k ine t i c paramete rs . AP22, Ramsey Cross ing , and Ohio
shales and kerogens exhibited principal discrete activation
ene rgi es of 54 to 57 kcal/mol, narrow d i s t ri b ut i on s , and Tmax
at 25C/min heat ing r a t e around 480C. Kimmeridge and
Phosphoria shales and kerogens exhibited kinetic parametersty pi ca l of type II source rocks pr in ci pa l di s cr e te
ac t iva t ion energ ies of 54 to 57 kca l /mol , b road
di st r i bu t i on s, and Tmax at 25C/min around 459C.
The discrete distr ibution kinetic parameters were use to
calculate oil generation at laboratory and geological heating
r a t e s . Each shale and correspondi ng kerogen ex hi bi te d
generation curves and 50% generation temperatures that werevery si mi la r. The pr in ci pa l di ffe re nc e was the kerogens
exhibited more oil generation at low temperatures compared to
th e corresponding sha l es . Some kerogens ex hi bi te d curve s
which were also shifted to slightly lower temperatures than
the corresponding shales.
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I (!
For these specific shales and kerogens, the results indicate
that kerogen isolation does little to effect the pyrolysis
kinetic parameters, therefore kerogen isolation may not be
necessary to derive valid kinetic parameters for some, and
perhaps most, samples.
INTRODUCTION
Kerogen pyrolysis kinetics has been the subject of much
research in recent years with the incorporation of laboratory
pyrolysis methods such as Rock Eval, hydrous,
thermogravimetric and more recently Pyromat pyrolysis to
provide data for various oil maturation models. High quality
kinetic analysis (and derived activation energy parameters)is essential for these models because of the need to
extrapolate from fast heating rates and high temperatures
found in the laboratory measurements to very slow heating
rates and relatively low temperatures found for the
geological extrapolation. Success of all this is, of course,
relies on the ability to accurately measure pyrolysis
behavior in the laboratory. In addition, this resulting data
must be generated under condition by which it can be
interpreted and translated to have geological relevance.
Whether laboratory pyrolysis can truly mimic geological
maturation still is debated.
One important and very practical issue is can kerogen
kinetics be measured on the \*'hole source rock or shale to
give meaniful results, or should these kinetics be measured
on kerogen concentrates where the mineral matter has been
chemically removed. . The effect of added mineral matter
common to many shale deposits on laboratory pyrolysis has
been studied in some detail alumina, bentonite, kaolinite,
calcite, illite, montmorillonite, quartz, dolomite (Horsfield
and Douglas, 1981), (Dembicki et al., 1983), {Katz, 1983),
{Dembicki, 1991). Evidence indicates that mineral matter may
?
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affect pyrolysis through pyrolysate yield and compound
distribution changes. What is not clear is the effect of
mineral matter on kinetic parameters. Dembicki (1991) found
that added mineral matter affected the kinetic parameters
found for kerogen concentrate pyrolysis, but it is not clear
if the study was looking at real effects or statistical
scatter, since the Umax was not affected significantly. Other
comparison studies between isolated kerogens and
corresponding source rocks have shown, in some cases, little
differences in the derived kinetic parameters (Jarvie and
Lundell, 1993).
To address this unresolved issue, we present the laboratorykinetic analyses by the Pyromat II micropyrolyzer of five
shales and related kerogen concentrates. The kinetic
parameters derived for the shales are compared to the
corresponding concentrate. In addition, the kinetic
parameters are utilized to extrapolate to geological
conditions to compare at what temperature ranges oil
generation is predicted to occur.
EXPERIMENTAL
Samples. Selected elemental analyses of the shale samples
are shown in Table 1. Some of these analyses have been
reported previously (Reynolds et al., 1991), (Reynolds and
Murray, 1991). All the analyses are on the whole, not dried
sample, so therefore the wt % C and wt % H include sources
other than organic. C, H, and N were done on a Leco 600
analyzer and wt % S on a Leco SC 132 analyzer. Wt % CO2 wasmeasured directly by acid treatment of the shale.
AP22 was from the Green River formation (Anvil Points Mine,
Colorado); Ramsey Crossing was from the Rundel Deposit
(Australia) , Ohio (Devonian) was from a Lower Huron member
core sample (3000 - 3800 ft) from well 20336 in Martin Co.,
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KY and was provided by George Claypool; Kimmeridge was from
the Draphne formation in the North Sea and was provided by
Birger Dahl (Norsk Hydro); and Phosphoria was from the Retort
Mountain Quarry in Beaverhead, Montana, and was provided by
George Claypool (USGS); kerogen concentrates were provided by
Alain Samoun (Lab Instruments).
Kinetic Analysis. The method of kinetic analysis using the
Pyromat II has been described in detail elsewhere (Braun et
al., 1991). The Pyromat II micropyrolyzer (Lab Instruments,
Kenwood, CA) measures hydrocarbon evolution utilizing a FID
detector. Normal sample size was approximately 4 mg (for
kerogen) to 10 mg (for shales). The temperature was measure
directly with a thermocouple in the center of -he sample
loaded in a quartz crucible. Kinetics were determined from
multiple runs at constant heating rates (nominally) three
50C/min, one 7C/min, and two lC/min runs were performed
for each kinetic data set. If Tmax values (temperature of
maximum rate of evolution) and profile shapes were not in
agreement, more runs at these heating rates were performed.
Kimmeridge and Phosphoria shales were examined previously
(Braun et al., 1991) using four heating rates (nominally 1,4, 15, and 50cC/min). Rate data were analyzed by using the
regression analysis program KINETICS (Burnham et al., 1987),
which contains several methods of accounting for a reactivity
distribution. The kinetic parameters used in this study were
determined by the shift-in-Tmax (yielding Aapprox and EapProx)
(Braun et al., 1991), modified Friedman (Friedman, 1963),
modified Coats-Redfern (Coats and Redfern, 1964), and the
discrete distribution (yielding Adiscrete a nd Ediscrete) (Braun
et al., 1991) methods.
RESULTS
Kinetic Analyses. Table 2 shows the complete listing of the
Friedman analyses for the shales and corresponding kerogens.
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The Friedman method is a fairly simple approach which assumes
the reaction rate is a function of conversion and
temperature. Activation energy is determined as a function
of conversion with no assumptions required about the
frequency factor. Comparing the 50% extent of reaction
activation energies (E5o%Frie
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Crossing shale exhibited plausible values of n and A (0.8 and
5-5 X 1014 respectively). However, the width of the reaction
profile is broader than a first-order reaction, requiring n >
1 for a single reaction, so the method is not internally
consistant. The other samples did not exhibit reasonablevalues, probably indicating that an n-th order reaction was
not being strictly followed.
The data was also examined by a modified Coats-Redfern (1964)
type analysis. The results for all the shales and kerogens
are listed in Table 3. The behavior is in good agreement
with the values calculated by the Friedman method. The 50%
extent of reaction activation energy values (ESO%C-R) frAP22
and Ohio shales and corresponding kerogens are within
experimental error, while the largest differences are
exhibited by the Kimmeridge shale and kerogen.
The behavior of the activation energy (calculated by the
Coats-Redfern method) as a function of extent of reaction for
the samples was very similar co that of Figure 1, with the
shales and corresponding kerogens being in close agreement.
Figure 2 shows the activation energy distribution calculated
by the discrete method and the associated frequency factors
as well as the activation energies and frequency factors
calculated by the shift-in-T^ax method for the shales and
kerogen concentrates. Figure 3 shows the evolution data for
the three different heating rates and the calculated fits of
that data from the discrete distribution analyses. Also
shown are the residuals of the least squares of the fits. Si
is the sum of the squares of weighted normalized rateresiduals, and L2 is the sum of the squares of weighted
integrated rate residuals. Casual inspection of Figure 2
shows immediately that, in most cases, there is good
agreement between the kinetic parameters of the shale and the
corresponding kerogen concentrate. Casual inspection of
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f
Figure 3 shows that the fits generated by the discrete
distribution agree very well with the generated data.
Table 4 summarizes the energies of activation of each sample
for convenience. Listed are Eapprox, principal discrete/
Eso%Friedman, and Eso% c-R- Also included is the calculated
(from the discrete distribution method) Traax at the 25C/min
heating rate.
The Eapprox, principal Ediscrete/ E50%Friedman/ and Sso%c-R are
all within experimental error for each shale and kerogen in
most cases. The exceptions are: the Eso%Friedman fr tn e Ohio
shale and Kimmeridge kerogen, and the Eso%c-R fr tne
Kimmeridge shale and Ohio kerogen are slightly higher than
the corresponding Eappr0x and principal Ediscrete*T n e
calculated Tmax at 25C/min heating rate differ by 3 C or
less in all cases.
The distributions in Figure 2 show some slight differences
between the shales and the corresponding kerogens. The a
value for the Ohio shale is much noticably than for the
kerogen. The shale exhibited early evolving material(Figure
3) which was intense enough in the lC/min profile that it
was deleted for the fitting procedure. This could
artificially affect a.
This low temperature evolving material could be due to a
variety of sources -- primarily unextracted bitumen and/or
mineral effects. Unextracted bitumen has been shown to
affect kinetic parameters derived from Pyromat II
measurements in shales (Reynolds and Murray, 1991), coals
(Reynolds and Burnham, 1993) and tar sands (Reynolds,
manuscript in preparation), primarily through broadening of
and coevolution with the principal pyrolysis peak. This
sample is particularly lean, which may be resonsible for a
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higher relative abundance of the bitumen. The effects of
mineral matter will be discussed below.
The Kimraeridge kerogen has a broader distribution than the
shale. This difference does not appear to be reflected inother parameters, including the quality of fits (Figure 3)
and calculated Tmax at 25C/min. However, in might be some
indication that there is a difference in some cases between
shale and corresponding kerogen samples.
Phosphoria shale and kerogen have discrete energy
distributions which are slightly different, which could
reflect difference in having mineral matter present or not.
However, both distributions are broad, and it would be
speculative at best to ascribe matrix effects to these minor
differences.
Oil Generation. Figure 4 shows the oil generation curves for
the shales and corresponding kerogens calculated from the
discrete distribution data at laboratory (lC/min) and
geological (3 C/m.y.) heating rates. In each figure, the
shale oil generation is indicated by solid lines, while thecorresponding kerogen oil generation is indicated by the
dashed line.
The AP22 shale and kerogen generation curves are almost
identical for both laboratory and geological heating rates.
The kerogen has a little more low temperature evolving
material which is imaginatively apparent when comparing the
discrete distributions and evolution data (Figures 2 and 3).
The Ramsey Crossing shale and kerogen have very similar
generation curves at l0C/min, with the kerogen slightly
shifted to lower temperatures compared to the shale (this is
also seen in the lower calculated T^* at the 25C/min heating
rate shown in Table 4). At the geological heating rate, the
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generation curves are also almost identical in shape, but as
in the laboratory case, the kerogen is shifted to slightly
lower temperatures compared to the shale.
The Kimmeridge and Ohio samples have almost identical
generation curves except for a little more early evolving oil
generated from the Kimmeridge kerogen in both laboratory and
geological heating rates.
At the laboratory heating rate, the Phosphoria kerogen has
more notable oil evolution at lower temperatures than the
shale, but eventually behaves identically as the shale
towards the end of the oil generation. The broad discretedistribution of the kerogen has more intense low energy
contributions than the shale, but has a similar pattern for
the high energy contributions which can account for this
behavior. The oil generation at 3C/m.y. heating rate shows
the kerogen and shale are much more similar, with the kerogen
crossing over the shale at approximately 30% generation.
This is consistent with the kerogen having a slightly higher
principal Ediscrete-
DISCUSSION
From the kinetic parameters above, and the oil generation
curves shown in Figure A, the shales and the corresponding
kerogen concentrates behave very similarly. In all cases and
at both the laboratory and geological heating rates, the
kerogens exhibited more initial oil generation than the
corresponding shale, and in some cases, the oil generationcurves of the kerogens are slightly shifted from the
corresponding shale. However, these differences are minor,
indicating for this limited data set, the kerogens behave
essentially the same as the shales in pyrolysis kinetic
determinations.
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J a r v i e and Lundell (1993) have re po rt ed th e di ff er en ce s
between whole rock and kerogen kinetics determined by Rock-
Eval using a discrete distribution method for a Naples Beach
ou tc ro p sample from the Monterey (Miocene) format ion. The
whole rock had a p r inc ipa l E^iscrete of 55 kca l/mol (12% of
the distribution) and a Adiscrete of 2.12 X 1015
1/sec. The
kerogen concentrate had a principal Eaiscreteof
53 kcal/mol
(12% of th e dis t r ibu t ion) and a A
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/
parameters by pyrolyzing mixtures of sedimentary minerals
with varying concentrations of a kerogen isolated from a
Kimmeridgian black shale. The kinetic parameters derived
indicated, at low concentrations, that quartz, calcite, and
dolomite shifted the activation energies to higher values,
while montmorillonite shifted the activation energy to lower
values than observed for the isolated kerogen. The minerals
which shifted the activation energies to higher values were
considered to be due to retention of pyrolysate, while the
minerals which shifted the activation energies to lower
values were considered to be due to catalytically assisted
pyrolysis.
Our results on the limited number of samples examined
indicates that kerogen isolation has very little effect on
parameters when determining overall pyrolysis kinetics. The
implication is that isolation of the kerogen from the shale
is not necessary when determining these types of kinetics.
Whether mineral matrix effects mentioned above indicate
isolation of kerogen is necessary for valid kinetics is not
obvious. Isolating the kerogen from the rock matrix does
cause a change in the kerogen-rock interaction because of theremoval of naturally formed associations between the two.
Because these associations have to be somehow important in
diagenesis, removing them by kerogen isolation may not be all
that appropriate. However, the chemical effects of the
mineral matrix probably are a lot different at reservoir
temperatures and geological heating rates than in laboratory
pyrolysis. Regardless, our results show for the samples in
this study, there is essentially no difference between
kinetic parameters determined on the whole rock or the
isolated kerogen, and that for these types of kinetic
determinations, the arguments about mineral matrix effects
probably do not apply.
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CONCLUSIONS
The examination of the pyrolysis behavior of selected Green
River, Rundel, Ohio, North Sea, and Phosphoria shales and
isolated kerogen concentrates shows that the derived kineticparameters and calculated oil generation curves are very
similar between the shale and the corresponding kerogen.
These results indicates that in some cases, kerogen isolation
is not necessary to determine valid pyrolysis kinetics on a
whole rock sample.
ACKNOWLEDGMENTS
We thank Ann M. Murray of Lawrence Livermore National
Laboratory for experimental assistance and Alain Samoun of
Lab Instruments, Inc., for the kerogen concentrates. This
work was performed under the auspices of the U. S. Department
of Energy by the Lawrence Livermore National Laboratory under
Contract No, W-7405-ENG-48. Partial support came from the
office of Basic Energy Sciences and a group of industrial
sponsors.
REFERENCES
Braun, R. L., Burnham, A. K., Reynolds, J. G. and Clarkson,
J. E. (1991) Pyrolysis kinetics for lacustrine and marine
source rocks by programmed micropyrolysis. .Energy and
Fuels, 5, 192-204.
Burnham, A. K., Braun, R. L., Gregg, H. R. and Samoun, A. M.
(1989) Comparison of Methods for Measuring Kerogen Pyrolysis
Rates and Fitting Kinetic Parameters. Energy and Fuels 3,
42-55.
Coats, A. W. and Redfern, J. P. (1964) Kinetic parameters
from thermogravimetric data. Nature 201, 68-69.
12
7/27/2019 Comparison of Kinetic Analysis of Source Rocks and Kerogen Concentrates by Burhan andn Reynolds
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Delvaux, D., Martins, H., Leplat, P., and Paulet, J. (1990)
Comparative Rock-Eval pyrolysis as an imoproved tool for
sedimentary organic matter analysis. Adv. Org. Geochem. 16(4-
6),1221-1229.
Dembicki, H., Jr., Horsfield, B., and Ho, T. T. Y. (1983)
Source Rock Evaluation by Pyrolysis-Gas Chromatography. AAPG
Bull. 67(7), 1094-1103.
Dembicki, H., Jr. (1991) The effects of the mineral matrix on
the determination of kinetic parameters using modified Rock-
Eval pyrolysis. Org. Geochem. 18(4), 531-539.
Espitalie, J., Madec, M., and Tissot, B. (1980) Role of
mineral matrix in kerogen pyrolysis: influence on petroleum
generation and migration. Bull. Am. Assoc. Pet. Geol. 64,
59-66.
Friedman, H. L. (1963) Kinetics of thermal degredation of
char-forming plastics from thermogravimetry. Application to
a phenolic plastic. J. Polym. Sci., Part C 6, 183-195.
Horsfield, B. and Douglas, A. G. (1981) The influences of
minerals on the pyrolysis of kerogens. Geochim. Cosmichim.
Acta 44, 1119-1131.
Jarvie, D. M. and Lundell, L. L. (1993) Hydrocarbon
generation and kinetics of the Monterey formation. In USGS
Cooperative Monterey Organic Geochemistry Study, C. M.Isaacs, Ed.
Katz, B. J. (1983) Limitations of 'Rock Eval' pyrolysis for
typing organic matter. Org. Geochem. 4(3/4), 195-199.
13
7/27/2019 Comparison of Kinetic Analysis of Source Rocks and Kerogen Concentrates by Burhan andn Reynolds
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Klomp, U. C. and Wright, P. A. (1990) A new Method for the
measurement of kinetic parameters of hydrocarbon generation
from source rocks. Adv. Org. Geochem. 16(1-3), 49-60.
Orr, W. L. (1986) Kerogen/asphaltene/sulfur relationships in
sulfur-rich Monterey oils. Org. Geochem. 10, 4 99-516.
Peters, K. (1986) Guidlines for evaluating petroleum source
rock using programmed pyrolysis. AAPG Bui. *70(3), 318-329.
Rose, H. R., Smith, D. R., Quezada, R. A., Hanna, J. V., and
Wilson, M. A. (1993) Role of minerals and additives duriong
kerogen pyrolysis. Fuel Proces. Tech. 33, 149-157.
Reynolds, J. G. and Burnham, A. K. (1993) Pyrolysis Kinetics
and Maturation of Coals from the San Juan Basin. Energy and
Fuels, 7(5), 610-619.
Reynolds, J. G., Burnham, A. K. and Mitchell, T. 0. (1994)
Kinetic Analysis of California Petroleum Source Rocks by
Programmed Temperature Micropyrolysis, submitted Org.
Geochem.
Reynolds, J. G., Crawford, R. W. and Burnham, A. K. (1991)
Analysis of Oil Shale and Petroleum Source Rock Pyrolysis by
Triple Quadrupole Mass Spectrometry: Comparisons of Gas
Evolution at the Heating Rate of 10C/min. Energy and Fuels,
5, 507-523.
Reynolds, J. G. and Murray, A. M. (1991) Pyromat II
micropyrolysis of source rocks and oil shales: effects of
native bitumen content content and sample size on Tmax values
and kinetic parameters. Lawrence Livermore National
Laboratory Report UCRL-ID106505 January.
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Table 1. Selected Chemical Analyses for Shales
Sample C,w t% H, wt % N,wt% S,wt% CC>2,wt% TQ C/wt%
AP22 16J0 TI 53 03 22l 9SRamsey Crossing
Ohio 3.6 0.8 0.3 2.4 0.8 3.4Kimmeridge 6.4 1.5 0.4 3.3 0.8 6.2Phosphoria 16.8 2.2 0.8 1.8 OS 16.6
All samples were ground/ whole, and not dried before analyses.
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Table 2. Friedman Analyses Tor Selected Shales and Kerogens
A (1/sec) E(kcal/mol) A (1/sec) E(kcal/mol) A (1/sec) E(kcal/mol) A (1/sec) E(kcal/mol) A (1/sec)
AP22 Shale Ramsey Crossing Shale Oil Shale Kimmeridge Shale Phosphoria
6.84 x 1013
7.02 x 1013
9.73 x 10131.51 x 1014
1.93 x 1014
3.22 x 1014
5.44 x 1014
1.57x1015
2.70 x 10lfi
52.8 (2.6)
53.3 (0.5)
54.0 (0.7)54.7 (0.5)
55.0 (0.5)
55.7 (0.2)
56.5 (0.0)
58.0 (0.6)
62.6(1.1)
6.86x1014
3.96 x 1014
4.40 x 1014
6.05 x 1014
6.94 x 1014
8.82xl0l4
1.08x1014
1.08 x 1014
6.22 x 1014
56.4 (3.0)
56.3(1.6)
56.6 (0.7)57.1 (0.4)
57.4 (0.2)
57.8(0.1)
58.3 (0.4)
58.7 (1.0)
58.4(1.6)
3.40x1010
2.43 x 1017
5.22 x 10143.57 x 1014
4.47 x 1014
6.72 x 1014
1.38x1015
5.58x1015
7.87 x 1015
41.6(79.8)
64.4 (2.5)
56.6 (0.4)56.3 (0.8)
56.7(1.5)
57.4 (2.0)
58.6 (2.9)
61.1 (4.9)
62.5 (7.8)
3.29x1012
3.33x1013
2.09x1014
5.01 x 1014
9.08 x 1014
1.71 x 1015
4.89 x 1015
1.07 x 1016
5.70 x 1015
48.0(1.8)
51.3 (0.6)
54.0(1.1)55.4 (1.5)
56.4 (1.8)
57.6 (2.2)
59.4 (2.2)
61.0 (2.3)
61.0 (2.5)
3.50 x 10]5
8.90x1014
1.31x1015
6.80 x 1014
7.30 x 1014
4.15 xlO' 4
3.14x1014
8.18x1014
2.03 x 1015
AP22 Kerogen Ramsey Crossing Kerogen Ohio Kerogen Kimmeridge Kerogen Phosphoria
2.99 x 1014
2.51 x 1014
3.97 x 1014
1.90x1014
1.27x1014
1.13x1014
1.23x1014
2.63 x 1014
2.68 x 1014
54.4 (3.4)
54.9 (1.5)
55.8 (0.4)
54.9 (0.7)54.5 (0.9)
54.4 (1.3)
54.5 (1.2)
55.7 (1.3)
59.3 (1.9)
6.07 x 1010
1.30x1014
5.89 x 1014
5.18x10144.79 x 1014
5.31 x 1014
7.32 x 1014
1.69x1015
1.80 xlQi6
42.9 (5.2)
54.0 (2.0)
56.5 (0.4)
56.5(0.1)56.5 (0.3)
56.8 (0.6)
57.4(1.0)
58.8(1.6)
62.8 (3.2)
1.96x1021
4.95 x 1015
4.85x1014
1.85x10141.46 x 1014
1.29xl0l 4
2.84 x 1014
6.73 x 1014
1.24 xlO1 4
74.3 (43.5)
59.2 (4.3)
56.4(1.8)
55.1 (0.5)54.8 (0.5)
54.6 (0.7)
55.9(1.5)
57.5(1.0)
56.0 (3.4)
1.37x1019
2.83 x 1015
6.50x1014
4.64x10143.96 x 1014
4,93 x 1014
9.66x1014
3.59x1015
2.10x1015
67.4 (2.9)
57.0 (0.7)
55.3(1.1)
55.1 (1.4)55.1 (1.5)
55.6(1.9)
56.9 (2.4)
59.2 (3.3)
59.3 (2.8)
5.46x1018
1.78 x 1016
6.49x1015
5.75 x 10154.99 x 1015
7.05x1015
9.78 x 1015
6.56x1015
1.95x1015
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Tabl e 3. Coats-Redfern Analyses for Selected Shales and Kerogens
A(l/sec) E(kcal/mol) A (1/sec) E(kcal/mol) A (1/sec) E(kcal/mol) A (1/sec) E(kcal/mol) A (1/scc)
AP22 Shale Ramsey Crossing Shale Ohio Shale Kimmeridge Shale
5.13 x 10"6.97 x 10
14
3.22 x 1014
2.15 xlO1.45 xlO
14
1.01 x 1014
6.94 x 10^34.66 x 10>3
4.27 x 10"
53.5 (6.5)53.1 (2.6)
53.4 (1.2)
53.9 (0.6)54.3 (0.2)54.7 (0.0)
55.1 (0.0)
55.6 (0.0)57.2 (0.5)
5.11x1015
3.62 x 10*5
1.75x10"
1.04 x 10"6.61 x 10
14
4.14 x 10
2.36 x 1014
1.25 xlO14
4.08 x 1014
54.0 (2.5)55.9 (2.5)56.3(1.6)
56.6(1.1)57.0 (0.8)57.2 (0.5)57.5 (0.3)57.8 (0.0)
58.1 (0.4)
8.55 x
4.02 x2.89 x
2.86 x3.56 x1.05 x4.72 x
2.90 x2.16 x
100
10251018
10*10"
10"
10*4
1014
1014
9.8 (133.5)85.6 (7.3)65.7(1.5)
60.8 (0.9)59.0 (0.9)58.3(1.2)58.3 (1.6)58.9(2.1)
60.5 (4.7)
1.11 x 1014
6.87x10"9.20xlO!3
1.32 xlOl41.67 x 10
14
1.74 xlOl4
2.22 x IOI4
2,76 xlO14
1.97 x 1014
48.4 (4.6)49.4 (2.5)
50.9 (1,8)
52.4(1.7)53.6 (1.7)54.6(1.9)
56.0 (1.9)57.7 (2.3)59.3(1.8)
Phosphoria
8.44x10162.47 x 10
]6
9.16x10"
2 .85x10"1.60x1015
3.91 x 1014
1.84 xlOl4
9.12 x 10138.08x10"
AP22 Kerogen Ramsey Crossing Kerogen Ohio Kerogen Kimmeridge Kerogen Phosporia K
1.24x1017
4.03x1015
1.53X10"
7.16 xlOl4
3.09 x 10l4
1.34 xlOl4
6.02 x 1013
2.76 x 1013
1.34x1013
57.2 (6.4)
55.2 (3.0)
55.3(1.9)
55.4(1.3)
55.3(1.1)
55.1(1.1)54.9(1.2)
55.0(1.2)
55.7 (0.5)
8.23 x 109
1.19x 10"
1.74 xlO14
2.94 x 10M
2.84 xl0i 4
2.18 xlO14
1.47 x 1014
9.67 x 1013
8.30x1013
35
47
52
54
55^
5556
57,
58,
5 (8.0)
.3 (5.2)
.3 (3.0)
3(1.8)
2(1.1)
8 (0.6)3 (0.1)
0(0.4)
6(1.4)
3.38 x 1026
2.74 x 1020
1.85 x 1017
1.08 x 1016
2.02 x 10"
5.06 xlO1.84 xlOl
4
8.19 xlO1 3
2.95 x 1013
84.0 (74.9)
70.0(12.0)
62.1 (5.5)
59.4 (3.3)
58.1(2.2)
57.1 (1.6)56.7(1.4)
56.7(1.4)
57.3 (0.4)
2.38 x 1025
3.19 x 1018
5.34 x 1016
6.41 x 1015
1.60x1015
5.89 xlOl4
2.84 x IOI4
1.90 xlOl4
1.25 xlO
80.4 (5.2)
62.9 (0.2)
59.0 (0.8)
57.3(1.0)
56.4(1.2)
56.1 (1.3)56.2(1.6)
57.0 (2.1)
58.4 (2.7)
3.55 x 1022
1.58 xlO1 8
1.04 xlO1 7
2.57 x 1016
9.80 x 1Q15
5.22x10"
3 .26x10"
1.70x10"
3.24 x 1014
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Table 4. Summary of activation energy values for shales and kerogens determined by th shift-in-Tmax (Eapprox) / discrete distribution
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FIGURE LEGENDS
Figure 1. Activation energy (determined by the Friedman
method) as a function of extent of reaction for: AP22 shale
- i AP22 kerogen , Ramsey Crossing shale ,
Ramsey Crossing kerogen y Ohio shale , Ohio
kerogen , Kimmeridge shale --, Kimmeridge kerogen
Phosphoria shale , Phosphoria kerogen .
Figure 2, Kinetic parameters determined by discrete
distribution and shift-in-Tmax methods, comparing shales and
kerogens.
Figure 3. Experimental data at selected heating rates andcalculated fits (determined by discrete distribution method)
comparing shales and kerogens. (Nominal heating rates for
Kimmeridge and Phosphoria shales: 1, 4, 15, and 50C/min; all
others: 1, 7, and 50C/min.)
Figure 4. Calculated oil generation curves (using discrete
distribution kinetic parameters) for shales (solid lines) and
kerogens (dotted lines) at the laboratory heating rate of
lC/min, and geological heating rate of 3C/m.y.
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Figure 1
o
e
< 5
cLUc
oCO>o-.^y=^Vf:X-
/
0.2 0.4 0.6
Fraction Reacted
0.8
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Figure 2
8 0 -
6 0 -
4 0 -
2 0 -
AP22Oil Shale
2.1 X1014
I/Sec
0 - r
Eapprox =
53.7 (1.0) kcal/mol
Aapprox=
7.5 X1013
1/sec
a ' 0 . 0 % of Eapprox
6 0 -
4 0 -
2 0 -
T T
AP22Kerogen
Atfscrele-
9.7Xl013
1/sec
""11
3 =-
Eapprox=
53.5 (0.9) kcal/mol
^approx "
6.2 X1013
1/sec
0 = 1.4% Of Eapprox
_ _
1 1 1 1
4 0 -
3 0 -
2 0 -
Ramsey CrossingOil Shale
^discrete =
8.1 X1014
1/sec
Eapprox*56.8 (0.8) kcal/mol
appro* ~
5.1 X1014
1/sec
.a
5 0 -cul 4 0 -
*Z 3 0 -o
5s
2 0 -
1 0 -
0 -
Ramsey CrossingKerogen
Adtscretes
4.4 X 10t 4
i/sec
OhioKerogen
Adiscrele
2.1 X1 014
1/sec
4 0 -
3 0 -
2 0 -
1 0 -
KimmeridgeKerogen
^discrete =
2.6X1014
1/sec
I S -_ PhosphoriaKerogen
1 0 -
5 -
Adiscwte-
3.0X1015
1ftec
eapprox *
56.3 (0.0) kcal/mol
Aapprox=
4.2 X1014
1/sec
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Figure 3
200 250 300 350 4O0 450 500 550 600 200 250 300 350 400 450 500 550 600T*mp*raiurft, *C
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Figure 4
250 350Tempefa'jj'*. C
550
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