452

Energy & Fuels 1987,1, 452-458

Articles
Comparison of Methods for Measuring Kerogen Pyrolysis Rates and Fitting Kinetic Parameterst
Alan K. Burnham," Robert L. Braun, and Hugh R. Gregg
Lawrence Livermore National Laboratory, Livermore, California 94550

Alain M. Samoun
Lab Instruments, Inc., Kenwood, California 95452 Received April 20, 1987

We determine rates of product evolution during pyrolysis of several petroleum source rocks and isolated kerogens by nonisothermal techniques, including Rock Eval pyrolysis and pyrolysis-MS/MS, The resulting data are analyzed by nonlinear regression and simpler correlation techniques in terms of discrete and Gaussian-distributed activation energy models. We find that temperatures measured by standard Rock Eval analysis are too low by about 40 "C, resulting in kinetic expressions that are much too fast. Proper temperature calibration eliminates this problem. We explore the sensitivity of the kinetic parameters and extrapolation to geologic heating rates to uncertainty in the temperature calibration. We find that the discrete distribution model provides a superior fit to the laboratory data and probably a more reliable extrapolation to geological heating rates. We also assess how differences among kinetics for individual species relate to the activation energy distribution required for total hydrocarbon evolution. Kinetics from Rock Eval pyrolysis predict hydrocarbon generation rates intermediate between kerogen decomposition and oil expulsion rates during hydrous pyrolysis, but slight differences in activation energies result in similar predictions for a geological heating rate. Predictions of petroleum generation temperatures for lacustrine source rocks cover almost the same range as for marine source rocks.

Introduction Although the concept that petroleum formation is a kinetic process is well established, determining kinetic parameters for quantitative prediction has been elusive because of the complexity of the maturation process. Many experimental procedures and kinetic models have been tried.l Programmed microscale pyrolysis (e.g., Rock Eva12)and sealed-bomb hydrous pyrolysis3 are two currently popular experimental techniques, but they differ markedly in temperature-pressure history as well as the time that products have to undergo secondary reactions. Moreover, programmed pyrolysis typically measures total volatile hydrocarbons while hydrous pyrolysis measures expelled (floating) oil and bitumen (unexpelled extractable material), so it is not obvious how the kinetics from the two different experiments should relate. Hydrous pyrolysis would appear to be a better simulation, but the Rock Eval technique is much faster and cheaper. There are additional complications in choosing how to analyze the kinetic data. Lewan3has derived reasonable kinetic parameters for expelled oil from Phosphoria and Woodford shale assuming a simple first-order reaction. In contrast, other workers have found that an activation energy distribution is needed for some aspects of product evolution from coal,4Green River oil shale: and isolated
Work performed under the auspices of the U.S.Department of Energy by the Lawrence Livermore National Laboratory under Contract No. W-7405-ENG-48.
0887-0624/87/2501-0452$01.50/0

kerogens of various types.2*6 We have shown that the effective activation energy derived by assuming no distribution is strongly influenced by the distribution if actually present, and ignoring even a small distribution would cause problems in extrapolating the rate to geologic temperatures.' However, the mathematical complexity and computer requirements for treating activation energy distributions have limited their use. In this paper, we have started a systematic comparison of different techniques for measuring and deriving product formation kinetics. This work includes writing an easyto-use computer program for determining either Gaussian or discrete activation energy distributions. A t this stage, most of our kinetic results are from the Rock Eval I1 instrument, which is commonly used in the petroleum industry. However, initial pyrolysis-MS/MS experiments and both p ~ b l i s h e and ~ ~ ~ ~ d ~ unpublishedlOJ1kinetic data
~~

(1) Two good reviews, by D. W. Waples and B. Horsfield, are contained in: Aduances i n Petroleum Geochemistry, Brooks, J., Web, D., Eds.; Academic: New York, 1984; Vol. l.,pp 7-68, 247-298. (2) Ungerer, P.; Espitalie, J.; Marquis, F.; Durand, B. In Thermal Modeling in Sedimentary Basins; Burrus, J., Ed.; Technip: Paris, 1986;

pp 531-546. (3) Lewan, M. D. Philos. Tram. R. SOC. London, A 1985,315,123-134. (4) Howard, J. B. In Chemistry of Coal Utilization; Elliot, M. A., Ed.; Wiley: New York, 1981; 2nd Suppl Vol.; pp 665-784. (5) Campbell, J. H.; Gallegos, G.; Gregg, M. Fuel 1980, 59, 727-732. (6) Tissot, B.; Espitalie, J. Rev. Inst. Fr. Pet. 1975, 30, 743-777. (7) Braun, R. L.; Burnham, A. K. Energy Fuels 1987, 1, 153-161. (8)Campbell, J. H.; Koskinas, G. J.; Stout, N. D. Fuel 1978, 57, 372-376.

0 1987 American Chemical Society

Kerogen Pyrolysis Rates and Kinetic Parameters

Table I. Chemical Analysis of Samples anal., % tot N acid COz org C tot S SO4 0.3 22.2 9.9 0.3 17.1 0.5 10.9 0.0 0.7 1.0 0.2 4.2 2.2 0.0 2.0 0.2 1.3 0.9 0.2 1.0 11.1 4.4 0.0 0.8 0.4 6.2 3.3 0.7 0.5 0.8 16.6 1.8 0.1 0.7 0.8 15.4 3.3 0.2 0.8 3.8 17.0 1.7 0.2 3.3 11.0 0.8 0.7 0.0

Energy & Fuels, Vol. 1, No. 6,1987 453

sample AP22 AP25 NAIL1 NAIL8 NAKY KIMR

tot C 16.0 15.6 4.5

1.8

PHOS
WDFRD MMNG FSHN
a

11.4 6.4 16.8 15.6

18.1

tot H 1.4 1.6 0.8 0.7 1.4 1.5

2.2

FeS 0.1 0.1 0.2 0.0 0.2 0.1

0.4 0.0

FeSz
0.4

org S 0.2 0.3 0.5 0.3 1.0 0.8 0.3 0.2

org S/org CQ 0.006 0.026 0.016 0.021 0.023 0.019

0.006

1.8 3.8 2.3 0.5

2.2

11.9

1.6 2.7 2.0

0.9 0.5

0.008

Atomic ratio calculated before rounding. in direct contact with the bottom of the sample crucible, which is about 6 mm 0.d. by 6 mm long and weighs 1.5 g, including lid. Sample sizes were 50-100 mg of whole rock sample, depending on the organic content, and 10 mg of the isolated kerogens. Samples AP25 and AP22 were used as received (-20 mesh), but other samples were in larger pieces and were ground to -250 mesh. The FID detector a t the top of the furnace was maintained at 550 "C. The pyrolysis-MS/MS system consisted of a 4.5 cm i.d. by 23 cm long tube furnace connected to the capillary inlet to the MS/MS instrument by a condenser held at 120 "C and a transfer line held a t 150 "C. The spectrometer inlet was maintained at 200 "C. The temperature was controlled by a Lindberg proportional controller interfaced to an HP-85 computer and HP-3497A data acquistion unit. A 100-250 cm/min flow of argon, constant for a given experiment, provided an internal standard for the kinetic measurements and ensured that the product reached the mass spectrometer within a few seconds. The sample was contained in a stainless-steel reactor with a gas inlet at the top and a bottom frit for the gas exit. The Green River and New Albany experiments" used an approximately 60-g aliquot of -6/+50-mesh powder, similar in composition to those used in the Rock Eval experiments, although this Green River sample comes from tract C-a on the other side of the deposition center of the Piceance basin. For the Kimmeridge clay, the sample size was only 5 g and consisted of finely ground material that was pelletized and recrushed to a size of about 4 mm. Kinetic Fitting Program. A new computer program was written to fit kinetic data for an arbitrary thermal history to distributed activation energy models, and it has been licensed for commerical distribution. The user chooses options by either answering a series of questions interactively at a computer terminal or by creating an option file for batch processing. The program is written in standard Fortran 77, so it is potentially available on almost any computer. The program considers two types of distributed activation energy models. The discrete activation energy model allows the user to fit an average preexponential (frequency) factor and relative fractions and activation energies for up to 19 parallel fmt-order reactions. The Gaussian activation energy model allows the user to fix or fit for up to three parallel reactions any combination of the following parameters: preexponential factor, average activation energy, Gausgian distribution parameter, and reaction order. This model can be used, for example, to determine kinetics for both the SIare Szpeaks in a Rock-Eval-type experiment. For both models, if the experiments are at a series of constant heating rates, the program inspects the data and uses our very fast, approximate fitting procedure7 to determine possible initial guesses for the subsequent nonlinear regression analysis. This assures that the regression analysis will properly converge with a minimum of computer time. The numerical procedures for fitting the Gaussian model parameters have been described previ~usly.~ discrete model parameters are determined by The iterative linear-nonlinear regression, where the relative weighting factors for the parallel first-order reactions were calculated by using the constrained linear regression. The regression analysis time depends on the model chosen and the number of data pointa. For a typical data set consisting of three experiments with 100

for some of our samples enable some comparisons among different techniques and the beginnings of an understanding of the origins of activation energy distributions.

Experimental Section
Samples. A chemical analysis of the samples used in t i study hs is given in Table I. The sulfur speciation was made by measuring the sulfur content, corrected to a raw shale basis, of the residue from successive water, HC1, and HN03 treatments. The two Green River shales (Eocene) come from the Anvil Points mine in the Mahogany zone near Rifle, CO. AP25 is a blend approximately representing run-of-mine shale, while AP22 comes from a single rock. Both have been used in previous experiments from this l a b ~ r a t o r y . ~TheJKimmeridge clay (Cretaceous) was provided ~~ ~ by G. Speers (Norsk Hydro) and came from the 1800-m depth in a Norwegian North Sea well. The Phosphoria shale (Permian, Retort member) was provided by G. Claypool (USGS) and came from a quarry near Retort Mountain in SW Montana. Woodford shale (Devonian-Mississippian) was provided by M. Lewan (Amoco, sample WD-27) and comes from the Springer outcrop in Carter Co., OK. It is said to be very similar to that used in his hydrous pyrolysis s t ~ d yand our analytical procedure gave ,~ approximately the same organic sulfur to carbon ratio. New Albany shales (Devonian-Mississippian) came from both Illinois and Kentucky. J. Crockett (ISGS) provided a series of core samples from the 340-350-m depth of a well in Tazewell Co., E. The densities of the core pieces were calculated from dry and submerged weights. The two samples characterized in Table I represent the extremes of the density range (2.45 g/cm3 for NAIL1 and 2.53 g/cm3 for NAIL8). Sample NAKY came from Bullitt Co., KY, and is similar to batches used in oil shale processing research at LLNL. Samples of Maoming (MMNG) and Fushun (FSHN) oil shale were provided by Zhang Shi KO of Sinopec International. We also obtained type I and type I1 kerogens from Africa (source proprietary) for which we had no corresponding whole rock. All samples are nominally immature (vitrinite reflectance <0.5% where available). Apparatus and Procedures. Kinetic measurements were made with both Rock Eval I1 (Delsi Instruments) and a pyrolysis-MS/MS apparatus built at LLNL. Rock Eval II is a standard micropyrolysis apparatus used extensively in the petroleum industry to characterize the amount and type of organic matter in petroleum source rocks. Our MS/MS apparatus is a triple quadrupole type, where an ion mass selected by the first quadrupole decomposes in the second and the decomposition fragments are measured by the third.*' The Rock Eval I1 measurements were conducted both in the standard 25 "C/min mode and, for kinetic measurements, at a series of heating rates roughly equal to 5,16, and 50 "C/min. The s slowest allowed by Rock Eval II i 5 "C/min. Insulation was added to the 6 mm i.d. by 8 cm long furnace for the kinetic measurements to reduce noise. Also, a new, unsheathed thermocouple was placed (9) Shih, S.M.; o h , H.Y.Ind. Eng. Chem. Process Des. Deu. 1980, S
(10)Peters, K., unpubIished results, 1986. (11) Oh, M.S.;Crawford, R. W., unpublished results, 1987. (12)Wong, C. M.; Crawford, R. W.; Barton, V. C.; Brand, H. R.; Neufeld, K. W.; Bowman, J. E. Rev. Sci. Instrum. 1983 54, 996-1004. (13) Huss, E.B.; Burnham, A. K. Fuel 1982, 61,1188.
19, 420.

454 Energy & Fuels, Vol. 1, No. 6, 1987

Table 11. T ,

Burnham et al.
I
'
" ' 1

Values, Corrected and Uncorrected, Measured by Rock Eval I1 T OC , .

(25 "C/ min) 446 445 434 439 425 424 422 435 411

'

" ' 1

'

" I

Fits to individual experiments

std

(30 "C/

uncor
474 473 463 467 453 451 449 463 439

samole AP22 AP25 NAIL1 NAIL8 NAKY KIMR

mid"

true (30 "C/ min)

488 487 477 481 467 465 463 477 453

PHOS
kerogen I kerogen I1

true (25 "C/ min) 484 483 473 477 463 461 459 473 449
0.1
1.o 10

"The measured heating rate during the "25 OC/min" cycle was actually 30 OC/min. About 4 O C of the difference between measured and standardized values can be attributed to this difference in heating rate. points each, fitting to the discrete model takes about 0.1 min on a Cray-l,2 min on a MicroVAX, and 20 min on an IBM PC and generally takes less time for the Gaussian model. The program is capable of fitting to reaction rates, integrated reaction rates, cumulative reaction, or differentiated cumulative reaction. Since a different function is being minimized, fitting to the different quantitieswill result in slightly different kinetic parameters.' Both the Rock Eval and pyrolysis-MS/MS experiments measure reaction rate, not cumulative reaction. An incomplete separation of the SIand S2peaks and an uncertainty in the base line can introduce errors into the integrated rates, so the rate data were fitted directly for this work. We also noticed that fluctuations in the Rock Eval temperature data, attributed to furnace heater cycles, introduced a "noise" in the calculated rates that was not present in the experimental rates, apparently because the thermal mass of the sample and crucible damped the fluctuations. Moreover, the original 300 or so data points per experiment were more than required, so we smoothed the temperature data over 5 points and the rate data over 3 points and kept every third point. Results

100

Heating rate, "Clmin

Figure 1. Relationship between heating rate and 7- for Green ' River shale, calculated from several kinetic expressions derived from the data of Campbellaand Shih and S0hn.B The single points are from data in ref 9. Parameters that represent the average well are A = 1 X 1013s-* and E = 51 kcal/mol.
Table 111. Effect of Temperature Measurement Errors on the Quality of Kinetic Parameters Derived

. at 5, 16, , T and 50 OC/min, O C

base case: 410,431,453 case 1: 416, 437, 459 case 2: 404,425,447 case 3: 410,428,447 case 4 410, 434,459

A, s-l E, cal/mol at 10 OC/Ma, O C 4.4E13" 49960 132 6.1E13 50860 137 3.2313 49110 127 2.0316 58050 155 4.4Ell 43890 111

. , T

"4.4313 = 4.4 X 1013,etc.

Rock Eval Pyrolysis. All micropyrolysis techniques

suffer from a temperature measurement problem because it is difficult to imbed a thermocouple in the sample. This problem is particularly acute in the Rock Eval I1 instrument because the temperature profile is very nonuniform. Temperature is normally monitored by a platinum RTD on the outside of the furnace or a thermocouple below the sample. For conventional Rock Eval measurements, we followed the standard procedure of calibrating T with , , a measurement on IFP sample no. 37133. The difference between the measured and "standard" T value for this sample was added to other measured values to obtain the "standard" value given in Table 11. This assures consistancy with other users for maturity correlations, but does not ensure true temperatures required for meaningful kinetics. Our initial analysis of data a t multiple heating rates found, in agreement with Ungerer,2J4that the standard Rock Eval temperature calibration procedure gives temperatures far lower than the values, resulting in kinetic expressions that are much too fast. Because of the difficulty of measuring the true sample temperature, we decided that pyrolysis kinetics for Green River shale were well enough known from oil evolution experiments that it could be used as a standard. We used the kinetic expression of Campbell et a1.8 and a reanalysis of the data
(14) Ungerer, P. 'Notice D'Utilisation du Programme OPTIM", Report 33388; Institut Francais du Petrole: Paris, (London) 1985; p 15.

of Shih and SohnQto establish the relationship between T and heating rate shown in Figure 1. Slightly different , , values were obtained from the variety of kinetic expressions derived by different analysis procedures of the kinetic data, and T,, calculated by using A = 1 X 1Ols and E = 51 kcal/mol works well on average. In principle, the temperature correction can be a function of both furnace temperature and heating rate. The temperature dependence would be caused by a greater steady-state oven temperature nonuniformity a t higher temperature, and the heating rate dependence would be caused by different thermal response times for the sample and thermocouple. Before proceeding with the data analysis, we first consider the effect of different kinds of temperature measurement errors of T. Table I11 in, , dicates that an error which depends on heating rate causes a large error in the activation energy, resulting in a major problem when extrapolating to geological conditions. In contrast, a constant temperature measurement offset causes a calculated offset that is roughly independent of heating rate. Analysis of data for three data seta for sample AP22 and one data set for AP25 indicated that the temperature offset of T,, from the uncorrected thermocouple reading was 14 "C and independent of heating rate to within the exC perimental precision of *2 O for heating rates less than 50 OC/min. A few experiments a t 60 "C/min indicated a correction 3 "C lower. Because the standard Rock Eval calibration procedure generates a correction of about -28 "C, the true temperatures are about 42 "C higher than the standard reported value. Part of this difference is due to different heating rates, so the actual difference between true and measured temperatures is only about 38 "C. This correction agrees fairly well with the approximately 35 "C correction given by Ungerer.I4 However, the IFP correction increases with temperature (and consequently with heating

Kerogen Pyrolysis Rates and Kinetic Parameters

Energy & Fuels, Vol. 1, No. 6,1987 455

Table IV. Kinetic Parameters Determined by Nonlinear Regression to Discrete Activation Energy Model percent of sample characterized by given Eo Eo, AP22 AP25 NAILl NAIL8 NAKY KIMR PHOS WDFRD MMNG FSHN kerogen1 kerogen11 kcai/mol (2.2313)' (1,1313) (6.2312) (7.6313) (2.5310) (3.7312) (8.0311) (6.3314) (2.0311) (1.5E13) (3.1314) (7.7312) 38 1.4 39 0.1 0.2 0.4 40 0.2 1.4 41 0.6 82.8 0.4 1.6 42 6.0 0.2 1.0 0.3 43 10 . 7.7 4.0 1.0 44 3.6 0.5 1.5 6.4 73.1 0.8 0.1 45 0.2 0.7 22.6 11.9 0.9 4.5 46 1.1 24.8 2.5 0.5 13.4 0.9 47 3.7 0.9 1.0 17.6 25.1 0.2 0.1 18.8 48 5.4 2.4 15.7 31.4 8.8 0.9 1.6 4.0 0.4 6.3 49 51.9 1.9 3.2 27.8 0.6 0.2 28.4 50 17.7 0.8 5.6 2.9 18 . 2.7 26.4 51 11.3 92.0 5.0 1.1 1.7 77.2 1.0 1.9 52 92.3 1.0 6.6 4.1 0.4 8.5 53 0.7 54.0 1.7 0.9 6.1 8.6 0.3 54 37.9 1.2 0.3 15.7 55 0.4 0.8 0.2 15.7 2.3 56 0.4 1.1 28.2 92.6 57 0.3 1.3 7.8 2.3 58 9.2 4.4 59 0.7 60 4.1 64 0.4
'A (e-') is given in parentheses; 2.2313 = 2.2
X

etc.

rate as in case 4 in Table 111),so use of that correction would lead to lower activation energies with a resulting prediction of lower petroleum formation temperatures. Our observation that the temperature correction for T , , is independent of heating rate implies that changes in the steady-state and transient temperature effects cancel for this special case. This does not mean, however, that the temperature correction should be independent of temperature for a given heating rate. Experiments with a thermocouple above and below the sample container suggested that the temperature correction for a given heating rate should be a few degrees higher a t higher temperatures. However, in the absence of enough firm data to derive a complex temperature correction, we stayed with the constant correction. This should not affect the average activation energy, which by definition is referenced to our standard value for Green River shale, but it may result in distributions that are slightly narrower than the true value. However, this limitation is probably less severe than the assumption of a constant preexponential factor, which causes an error in the opposite direction. The samples were actually run in sets a month or two apart. For most sample sets, sample AP22 was included as a standard. However, it w s not run for a set containing a samples KIMR, PHOS, and NAIL8 or a set containing the MMNG and FSHN samples. The correction for these samples was made from comparison of T , a t higher , heating rates when the samples were run back-to-back with sample AP22. We estimated a temperature correction of 16 OC for the set containing sample KIMR and about 10 "C for the Chinese samples, so kinetics for these samples are slightly less reliable. A summary of our results for the discrete and Gaussian models is shown in Tables IV and V. All samples have average activation energies in the 42-56 kcal/mol range, which makes sense chemically. The principal activation energy for the discrete model averages 0.8 kcal/mol higher than Eo for the Gaussian model, and the standard deviation of differences between the energies from the two models is 1.6 kcal/mol. The approximate method for estimating the Gaussian model parameters gives, on the

Table V. Kinetic Parameters Determined by Nonlinear Regression Analysis Using the Gaussian Activation Energy Model, Assuming a Reaction Order of 1 . at 10 "C/Ma, , T "C E, 0 1 sample A, cal/mol % of Eo Gaussian discrete 0.1 142 155 AP22 2.8312' 48996 AP25 1.9312 48494 0.5 140 152 NAILl 49223 6.2311 1.9 152 139 3.3313 52251 NAIL8 1.3 151 157 NAKY 4.8E10 42312 1.6 109 107 KIMR 4.8312 48550 2.5 135 131 PHOS 4.0311 45042 3.8 119 123 WDFRD 2.3314 53928 3.7 150 161 MMNG 45088 3.4311 1.7 121 118 FSHN 5.9312 49768 1.3 142 147 kerogen I 1.7314 55190 0.0 164 169 kerogen I1 6.7312 48817 3.7 132 140
"2.8312 = 2.8
X

etc.

average, an activation energy between those determined by nonlinear regression using the Gaussian and discrete models. There was essentially no correlation between the standard error of energies determined by the approximate method from the shift in T with heating rate and the , , changes in Eo upon nonlinear regression with the Gaussian model. The value of u determined by approximate method is systematically 0.16% of Eo lower than that determined by nonlinear regression, with a standard deviation between the two methods of 0.4% of E,,. All distributions are relatively narrow compared with those in the original Tissot-Espitalie schemes6and are roughly consistent with more recent re~u1ts.l~Because of a greater number of parameters, the discrete distributions fit the data better, as shown in Figure 2. The mean squared residuals were typically 2-3 times lower for the discrete model. Pyrolysis-MS/MS. It has been shown previously that different chemical species are formed a t different rates during p y r ~ l y s i s What is lacking is a quantitative un.~~~ derstanding for various kerogen types of how these dif(15) Ungerer, P.;Pelet, R. Nature 1987 327,52-54.

456 Energy & Fuels, Vol. 1, No. 6,1987

Burnham et al.

-5.

._ o'8
340 380 420 460

500 300 340 380 420 460 500 540 580 Temperature ("C)

1---

'

'

Discrete distribution Green River shale Kerogen II

/

Figure 2. Comparison of rate data for Green River ( A P 2 2 ) and Phosphoria shales heated at 5 OC/min to that calculated from the parameters of the Gaussian and discrete models. The mean residual s u m of squares of the discrete model is typically 2-3 times lower.
Kentucky
Green River

Temperature, " C

Figure 4. Reproducibility of Rock Eval kinetic predictions at a heating rate of 10 "C/Ma. Three of the Green River experiments were on sample AP22 and one on sample AP25.
a COz peak at or slightly above 500 "C, which is probably due to some kind of iron-containing carbonate. This peak is generally absent for Green River shale from the Anvil Points mine.13 These results will be described in more detail in a later publication that includes experiments at more than one heating rate.
300
400

500

600

300

400 500 600 Temperature PC)

300

400

500

600

Figure 3. Comparison of the n o r " d evolution rates of several species from Kimmeridge, Kentucky, and Green River shales heated at 4OC/min. Gas analysis was by on-line MS/MS, which allowed specific identification of toluene (92 91) and methyl thiophene (97 53). The dashed lines at the bottom are the rates of the individual components determined by Rock Eval pyrolysis.

ferent kinetics are reflected in the activation energy distributions derived from more global techniques, such as total hydrocarbon generation measured by Rock Eval or weight loss observed by thermogravimetric analysis of kerogen. We have initiated a series of pyrolysis-MS/MS experiments that should establish such an understanding. These experiments will be an improvement over previous pyrolysis-MS experiments because the MS/MS provides a more complete gas analysis and also allows a more definitive separation of molecular types, especially trace heteroatom-containing components, in both the oil and the gas. Initial results for a few species generated a t 4 OC/min are summarized in Figure 3. As expected, different species are evolved at different rates, and the Rock Eval kinetics agree generally with the average generation rates of the individual hydrocarbon-containing species, except methane. For Kimmeridge and Green River shales, methylthiophene is evolved a t a noticeably lower temperature than the normal hydrocarbons. However, it does not appear that the energy distributions are caused by the sum of the individual components, each described by a single activation energy, because even the profiles of individual components are broader than can be described by a single activation energy around 50 kcal/mol. For Kimmeridge and Kentucky New albany shales, the maximum water release rate comes between 500 and 550 OC, but it is close to 300 "C for Green River shale. All three samples have

Discussion Two important issues concerning the use of laboratory experiments to predict petroleum generation conditions are, (1)is the Arrhenius equation valid over such a wide temperature range and (2) can the parameters be measured well enough to be reliable? The first cannot be answered definitively by theoretical arguments, and we can only say that empirical evidence thus far is very encouraging.15Je Assuming that gross temperature measurement problems can be overcome by procedures such as those developed in this work, the second issue boils down to whether the activation energy can be measured accurately enough. A minimum requirement, of course, is adequate precision. This is most easily tested for our results by comparing geological predictions for replicate experiments. Figure 4 shows the predictions from the four separate runs on Green River shale and two runs on kerogen 11. The same temperature correction was made for all data sets, so this is a true test of precision. In contrast, the absolute accuracy is tied to the accuracy of our activation energy standard of 51 kcal/mol. The two additional runs on sample A P 2 2 that are shown in Figure 4 had a higher mean residual sum of squares than for all sets of runs included in Tables IV and V. Even so, the predictions using a given model are sufficiently close together that the major uncertainty in their application is probably limited to the geological model. One concern is that for Green River shale, the Gaussian C model predicts major hydrocarbon generation 10-15 O lower than does the discrete model, caused by a lower activation energy. The principal activation energy from the discrete model is much closer to our standard value
(16) Sweeney, J. J.; Burnham, A. K.; Braun, R. L. AAPG Bull., in

press.

Kerogen Pyrolysis Rates and Kinetic Parameters

Phosphoria

Energy & Fuels, Vol. 1, No. 6,1987 457

510

25

290 310 330 350

25 240260280300320340 Temperature, "C

25

300

320

340

360

Maturity, % of S, reacted

Figure 5. Predictions of the shift in T with maturity, calcu, , lated by using the discrete model kinetic parameters with a prereaction at 10 OC/Ma.

published3and unpublished1 hydrous pyrolysis data for three source rocks. The predictions are intermediate between total product formation and oil expulsion, which are fairly similar for Green River shale. We previously gave correlations between the value of sigma for the Gaussian activation energy distribution model and both the shift in Rock Eval T,, and an increase in the effective activation energy with m a t ~ r a t i o n .All ~ samples investigated here fall within the range of those correlations. Figure 5 shows the corresponding prediction of the TmB, shift effect for Green River, Woodford, Kimmeridge, and Phosphoria shales for results from the discrete activation energy analysis. It has been assumed to this point that the high-temperature, programmed pyrolysis measures kinetic processes relevant to natural petroleum formation. However, differences in pyrolysis conditions and product composition have raised some questions. The hydrous pyrolysis technique of Lewan3is generally considered to be closer to the conditions of natural petroleum formation, so a comparison of Rock Eval with that technique would be instructive. Figure 6 shows a comparison of total hydrocarbon generation predicted by Rock Eval kinetics (discrete model) with the bitumen formation, oil expulsion, and kerogen consumption during hydrous pyrolysis of Green River,lo Woodford,3 and Phosphoria3 shales. The Rock Eval predictions agree well with oil expulsion only for Green River shale. The predictions for Woodford and Phosphoria shale are obviously between bitumen formation and oil expulsion. In addition, our kinetics for Kimmeridge clay predict faster hydrocarbon generation than the reported quantities of expelled oil and gas from hydrous pyr01ysis.l~ There are several related differences between Rock Eval and hydrous pyrolysis that could lead to'different predictions, particularly for non Green River samples. First, the samples are not identical, but they should be similar enough for this not to be a factor. Second, Rock Eval measures t t l volatile oil and gas while hydrous pyrolysis oa measures only light oil that is expelled from the rock by some ill-defined process. The oil-to-gas hydrocarbon ratio for Green River shale is greater than 10, while it is probably only about 5 for the Phosphoria and Woodford shales, so gas generation would have a greater influence on Rock Eval kinetics. However, primary gas, particularly methane, is evolved at a higher temperature than 0il,5913 which would tend to make Rock Eval kinetics slower than hydrous pyrolysis, just the opposite to what is observed. Delay of oil release in Rock Eval due to absorption on dehydrated clays generated by high-temperature pyrolysis has also been proposed,17J8but again, the effect is in the wrong direction. Instead, it appears that it is generally easier for oil to evaporate in a Rock Eval experiment than to be expelled in a hydrous pyrolysis experiment, so evolved
(19). Winters, J. C.; Williams, J. A.; Lewan, M. D. In Aduances in Organic Geochemistry; Bjoroy, M., et al., Ed.; Wiley: Chichester, England, 1981;pp. 524-533.

Figure 6. Comparison of Rock Eval kinetic predictions with

of 51 kcal/mol and the 52.4 kcal/mol used successfully to model petroleum formation from Green River shale in the Uinta basin,u so it is probably more reliable. Fortunately, the predictions of the Gaussian and discrete models are generally closer for other samples (Table V). In fact, a Student's t test for paired observations indicates that the difference between the discrete and Gaussian model activation energies is statistically significant a t the 90% confidence level when all 10 samples are considered but is statistically significant only at the 60% level when the two Green River samples are eliminated. The variation in reactivity of the Devonian samples (WDFRD, NAKY, NAIL1, NAIL8) spans a large fraction of observed range, although all are immature. The activation energy for sample NAKY is very low, for some unknown reason. Extending the data to lower heating rates would give us more confidence in this value. The reactivity trend of the New Albany samples may be due to mineral adsorption effect,17J8but this will require further measurements on isolated kerogens to test it. In a related matter, can differences in activation energies cause the reactivity ordering of different source rocks to be different a t laboratory and geological heating rates? The temperatures of maximum reaction rate shown in Tables I1 and V indicate that this may occur. For example, the reactivity of Woodford shale is comparable to that of Kimmeridge clay a t laboratory rates, but it is more similar to Green River shale under geological heating rates. However, we hesitate to attach too much significance to these values without verification in a geological setting. One interesting contrast to the implications of previous work2*6J6 that our activation energies are not characis teristic of whether the sample was deposited in a lacustrine or marine environment. Although the activation energy distributions derived for our lacustrine samples (AP22, AP25, MMNG, FSHN, and kerogen I) are typically narrower than those of the marine samples, the principal activation energies for the two environments extend over almost the same range. This results is predided petroleum generation temperatures for the two types that span almost the same range. This conclusion assumes that the minerals have had no effect, as discussed above. More work, including more thorough characterization by standard petrographic and modern spectroscopic techniques, will be required to determine the relationship of the kinetic parameters to depositional environment and chemical structure.
(17)Espitalie, J.; Deroo, G.; Marquis, J. Reu. Znst. Fr. Pet. 1985, 40, 775-777. (18)Peters, K.; AAPG Bull. 1986, 70, 318-329.

458 Energy & Fuels, Vol. 1, No. 6,1987

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Burnham et al.

0.9

.-

-8
L

0.8

0.7

0.6

._ 0.5

i
Temperature, "C

Figure 7. Comparison of predictions of Rock Eval and hydrous pyrolysis kinetics at a heating rate of 10 OC/Ma Both the discrete and Gaussian parameters from Rock Eval predict that hydrocarbon generation is spread over a wider temperaturerange than predicted oil expulsion from hydrous pyrolysis, but the temperatures for half-conversion are within about 5 O C .

Rock Eval hydrocarbons include some of what is defined as bitumen in hydrous pyrolysis. A closer look a t Figure 6 reveals the cause of the difference between Green River and the other two samples. The total product formation, as calculated from the amount of residual kerogen, tracks bitumen formation for Phosphoria and Woodford shales, but it is much closer to expelled oil formation for Green River shale. In fact, it appears that the Rock Eval predictions are fairly close to midway between kerogen disappearance and oil expulsion for all three samples. The difference is that nearly all of the Woodford and Phosphoria kerogen has reacted by the time the bitumen intermediate reaches its maximum concentration, while only about 30% of the Green River kerogen has reacted by the same time. It is not yet clear

whether this is a real difference in mechanism or whether the higher temperatures required for Green River kerogen pyrolysis have largely eliminated the mass-transport limitations for oil expulsion. In support of the fiist possibility, it is possible that conversion of kerogen to bitumen is due to breaking of oxygen-containing linkages between more refractory structures and that the higher oxygen content of marine kerogens enables more soluble macromolecules to be formed prior to cracking t o oil. Ironically, the differences between the hydrous and Rock Eval pyrolysis kinetics are less pronounced a t geological heating rates than in the laboratory because the Rock Eval expressions have slightly higher average activation energies. Depending on whether the Gaussian or discrete model is used, the Rock Eval predictions agree with the hydrous predictions in the 5 0 4 0 % conversion range, as shown in Figure 7. We are not yet quite sure what this means or if it is generally true. Further clarification of how kinetics from laboratory experiments relate to natural petroleum will require a thorough comparison between the amount and composition of hydrocarbons formed in laboratory experiments and in a geologic setting.

Acknowledgment. The authors thank those who provided samples for this work, K. Peters for helpful discussion during the initial stages and for providing the hydrous pyrolysis data on Green River shale prior to publication and M. S. Oh and R. W. Crawford for providing unpublished pyrolysis-MS/MS data on Green River and New Albany shales. We also acknowledge R. Swansiger for the chemical analysis and the help of K. Foster and R. W. Crawford on the pyrolysis-MS/MS experiment on Kimmeridge clay. Finally, we appreciate the help of F. N. Fritsch in deriving an efficient algorithm for treating the discrete distribution regression analysis. This work was supported by the USDOE Offices of Basic Energy Sciences and Fossil Energy.