Guidelines for Evaluating Petroleum Source Rock Using Programmed Pyroly: K. E. PETERS" ABSTRACT Rock-Eval pyrolysis is used to rapidly evaluate the petro- leum-generative potential and thermal maturity of rocks. Accurate conclusions require pyrograms every 30-60 ft (9-18 mp, understanding of interpretive pitfalls, and sup- porting data, such as visual kerogen, vitrinite reflectance, ‘and elemental analyses. ‘The generative potential of coals is commonly overesti- mated by pyrolysis and is best determined by elemental analysis and organic petrography. Most coals show high 52/83 (>5) and low HI values (<300 mg HC/g TOC). Migrated oil and mud additives, which alter Rock-Eval data, can sometimes be removed by special processing. For immature rocks, bimodal S2 peaks and PI values over 0.2 indicate contamination. Pyrolysis downgrades organic-poor, clay-tich rocks, which show lower HIl and higher T,., values than isolated kerogen because of adsorption of pyrolyzate on the clays. ‘Tay Values for small S2 peaks (<0.2 mg HC/g TOO) are unreliable. T,, is affected by maturation, organic matter ‘ype, contamination, and the mineral matrix. S3is sensitive to inorganic and adsorbed carbon dioxide, ‘and to instrumentation problems. Acidification of carbon ‘te-rich samples and proper maintenance improves S3 mea- surement, Constant sample weights (100 mg) are recommended. Belowa threshold weight, Ty. increases by up to 10°C, and other parameters decrease. Organic-rich samples, which ‘overload the detector, can be diluted with carbonate. Detec- {or linearity is determined by pyrolyzing various weights of an organic-rich rock. INTRODUCTION AA basic problem in petroleum exploration is how to assess the petroleum-generative potentials of prospective source rocks. Rock-Eval pyroysis of whole rock (Espitaliéet al, 197) ‘©Copyright 1986, The Anarican Associaton of Petrleum Geologist. righ recone Manuscript ceva May 20,1905: acopted December 2,198. ‘This paper was pecertd a the 183th National Meeting of he American (Chemical Society. Symposium on Organic Geochemistry of Humic Sub stareos, Kreger ard Coa, Phiadobna Renoytvania, August 2-31, 568 "Chavon Ol Feld Resesich Company, PO. Box 46, La aba, Cairns cosa! Tihank. J Domaison,W.G. Dow, R.A. Sturt 8. A.Patiarson, AR. Day sand LW, Jones Yor crisques of the manuscript anc Cheven OW Fld Reseatct Company fo perissione pubis provides information on the quantity, type, and thermal matu- rity of the associated organic matter (OM), Pyrolysis is defined as the heating of OM in the absence of oxygen, to yield organic compounds. In Rock-Eval pyrolysis, pulverized samples are ‘gradually heated under an inert atmosphere. This heating cis- till the free organic compounds (bitumen), then cracks pyro- Iytic products from the insoluble OM (kerogen). In some laboratories, the method has replaced extraction techniques for separating these materials because i is faster, involves less ‘manpower, an requires only small samples. This paper provides guidelines for understanding and intr- preting, Rock-Eval pyrolysis data. Guidelines are needed ‘because pyrolysis is widely accepted among exploration geolo- gists as rapid and effective means of characterizing the qual- ity and thermal maturity of prospective source rocks. Although the method is generally straightforward, the simplic- ity of the data occasionally can be misleading. Thus, this paper also attempts t0 define the pitfalls in interpreting pyrolysis results DESCRIPTION OF PYROLYSIS METHOD Instrumentation Various Rock-Eval pyroanalyzers are commercially availa: ble. The Rock-Eval I pyroanalyzer was designed by the Institut Frangais du Pétrole and built by Girdel, Inc. Two similar ver- sions of the Rock-Eval Il were produced by independent com- panies: Delsi, Inc., and Geocom, Inc. Compared to the Rock-Eval I, both Rock-Eval Il units are easier to operate and. troubleshoot, and provide more analyses per unit time. The Rock-Eval II (from Delsi, Inc.) combines pyrolysis analysis with the capability of determining total organic carbon. The Rock-Eval III (Oil Show Analyzer) differs from the Deli Rock-Eval Il in that it analyzes gas and oil separately and does ‘not measure carbon dioxide. This paper discusses Rock-Eval 1 analyses but is generally applicable to the other instruments. Obviously, an analysis of Rock-Eval data must consider the limitations of the instrument, such asthe linear range of detec- tors and tolerances of the integrators. Because of variations between instruments and accessories, this aspect will not be dis- ‘cussed but should be considered by each interpreter for the particular apparatus used Operating Conditions Operating parameters for the Rock-Eval instruments are similar to those described in Clementz etal (1979). Samples of ground whole rock weighing up toabout 100mgare pyrolyzed 318K.E. Peters, at 300°C for 3-4 min, followed by programmed pyrolysis at 25°C/min to $50°C, both in a helium atmosphere. Allowing time to cool the oven, each analysis requires about 20 min. Measured Parameters ‘The Rock-Eval II technique provides several measurements (Epitaié etal, 1977) (Figure 1). flame ionization detector (FID) senses any organic compounds generated during pyroly- sis. The fist peak (SI) represents milligrams of hydrocarbons that can be thermally distilled from one gram of the rock, The second peak (S2) represents milligrams of hydrocarbons gener- ated by pyrolytic degradation of the kerogen in one gram of rock. (Although the literature expresses SI and S2 in mili- grams of “hydrocarbons” per gram of rock, the FID also senses nonhydrocarbons provided carbon atoms are present.) ‘The third peak ($3) represents milligrams of carbon dioxide generated from a gram of rock during temperature program- ming up to 390°C, and is analyzed by thermal conductivity detection (TCD). In some United States publications, S1, $2, and S3 are respectively referred to as PI, P2, and P3. During pyrolysis, the temperature is monitored by a ther- mocouple. The temperature at which the maximum amount ‘of S2 hydrocarbons is generated is called T... ‘The hydrogen index (HI) corresponds to the quantity of pyrolyzable organic compounds or “hydrocarbons” (HC) from S2 relative tothe total organic carbon (TOC or C.,) in the sample (mg hydrocarbon/g organic carbon = mg HC/g Cap. The oxygen index (ON) corresponds to the quantity of carbon dioxide from S3 relative to the TOC (me COs/s Ca). ‘The production index (PI) is defined astheratioS1/(S1 + S Pyrograms Interpretation of Rock-Eval data requires access to the pyrograms. Figure 2 shows atypical program from the Rock- Eval Il unit. The temperature profile has been offset relative to the FID trace (6 mm on actual pyrograms) so that the dual ‘pens do not interfere. For reference, the beginning ofthe iso- thermal period at 300°C (noted by an asterisk in the figure) corresponds temporally with the first sharp increase in FID response to SI. Note that parameters are reported other than the traditional display of SI, S2, and S3 peaks and oven-iem- Perature profile. These include ID number, day and month, time of day, TOC (i known), sample weight (mg), and detec- ‘or attenuations. The two rows of numbers immediately above the pyrogram are percentage of scale and oven temperature 0). Following asample analysis and entry of such parametersas, sample weight and TOC, the system calculates S1, S2, $3, and Ta Atthe end of each Sequence of samples, a histogram and summary report can be printed. In Figure 2, the first number to the right of SI and S2repre- sents mg HC/g rock. The first number to the right of S3repre- sents mg CO,/g rock. The second number to the right of SI, 'S2, and $3 represents the peak area (“area counts”) measured by the integrator. For example, the S2 peak consists of 4.273 x 10° area counts, equivalent 10 2.793 x 10! mg HC/g rock. 319 /\ Bearer) oe SP uo Stieatein no [sine copatee Figure 1_Schematic of pyrogram showing evolution of organic compounds from rock sample during heating (increasing time {rom left to right). Important measurements include St, $2, $3, and T,,.- Hydrogen and oxygen indices are calculated as shown, “Unknown” indicates that the sample is from an active study and isnot a reference standard. The standard used at Chevron. is a homogenized composite of various rocks. APPLICATIONS OF ROCK-EVAL TO GEOLOGIC PROBLEMS Because Rock-Eval pyrolysis is rapid (20 min) and requires only small samples (100 mg), itis commonly used at the well site to screen large numbers of core and ditch-cutting samples for further study. However, critical interpretations should always be supported by additional geochemical analyses (Peters et al, 1983). Rock-Eval pyrolysis can be used to describe the petroleum generative potentials of prospective source rocks by providing information about their OM: (1) quantity, (2) type, and (3) —_— oo Dey = 7289900 Taree sess Geocom Rock-Eval I FO Atenuaton = 32 EO Atonaston = 32 ow on o* 10 wee | se 0 Reaponee = 7m 82 | i TOD Rewponae| ——e | wees Teroerdure | wrest Tou = oe S1'> A300 +00 Sum = +0.502+04 S2= 22706 $01 Sum = 14275405 Sb = s 45216 01 Sum = 12264403 Figure 2—Typical Rock-Eval If pyrogram and report showing oven-temperature profile, FID (S1 and 2), and TCD (S3) responses (increasing time from top to bottom). Asterisk near temperature curve designates isothermal heating period at 300°C. See text for explanation of annotations.320 thermal maturity (Tables 1-3) The method can also be used (0, indicate prospective reservoir rocks and locate the top (birthline”) and bottom (“deadline”) of the oi-generative “window.” Other applications include correlating reservoirs or source rocks between wells, mapping r rity o richness of source rocks, and predicting regions of likely petroleum accumulations within basins. Quantity of Organic Matier ‘Two useful measurements related to quantity of OM are the total organic carbon (TOC) and the fraction of TOC that is sgenerated as hydrocarbons and other compounds by pyrolysis (hydrocarbon index or HD). Tables 1 and 2 show how TOC, 2, and H1 are used to describe potential source rocks. Typically, TOC is determined by the direct combustion ‘method: crushed samples are acid treated in a filtering crucible to remove carbonate, combusted at about 1,000°C, and art led as carbon dioxide. Comparable results can be obtained by: (1) an indirect TOC method (total carbon minus carbonate carbon), or (2) a modified direct method using nonfiltering crucibles. These methods are discussed further in Peters and ‘Simoneie (1982). ‘The “Rock-Eval I plus TOC” (Deli In.) determines TOC by summing the carbon in the pyrolyzate with that obtained by oxidizing the residual OM at 600°C. For small samples (100, 1g), this method provides more reliable TOC data than con- ventional combustion methods, which require about 1-2 g of ‘ground rock. However, mature samples, where vitrinite reflee- tance (R,) is more than about 1%, yield poor TOC data when determined by the Rock-Eval III because the temperature is insufficient for complete combust ‘TOC is usually greater than the sum of the pyrolyzable car- bon in Si, $2, and S3. For example, a rock containing abun- dant graphite and no other OM will show a large TOC but ‘essentially no pyrolysis response. Pyrolysis is useful for predicting the quantity of organic ‘compounds that could be generated from a rock upon further maturation, An examples the excellent correlation of $2 with Fischer assay oil yield (Figure 3) Bienner and Espitalié (1980) have determined linear regressions between pyrolysis (SI. + 2) and Fischer assay yields for various types of OM. Types of Organic Matter ‘The mos familiar method of classifying OM typeiis the van Krevelen o atomic H/C vs, O/C diagram (Tissot etal, 1974). In this diagram (Figure 4), different types of kerogens are shown as Type I (very ol prone), Type II (0 prone), and Type IN @as prone). Type IV Ginert) Kerogens contain very litle >bydrogen and plot near the bottom of the figure. Tae thermal ‘maturation of each kerogen typeis described by pathways; the ost mature samples are near the lower left corner (ile Ihydrogen or oxygen relative to carbon in the kerogen) Espitali etal (1977) attempted to usethe Rock-Eval method to derive the same type of information conveyed by the H/C vs. O/C diagram, Because pyrolysis does not require kerogen ‘isolation, this method proved more rapid and less expensive Evaluating Petroleum Source Rock ‘Table 1. Geochemical Parameters Describing Source Rock Generative Potential Quantity Poor Fair Good Very good *Nomenclaie t= mg HCigreck 82 = mgNClgreck than elemental analysis. Espitalié etal showed that oxygen in the kerogen is proportional to the carbon dioxide liberated during pyrolysis ($3) and that the hydrogen content i propor- tional to the hydrocarbons liberated ($2). They defined the hhydrogen index (HI) vs. oxygen index (ON) plot (Figure 5), where HI and OI are ($2/TOC) x 100 and ($3/TOC) x 100, respectively This plot can be used to describe te rype of OM in any sample, but the results should be supported by micros- copy, elemental analysis, or both. The good correspondence bebween data in Figures 4. and $ is not typical for reasons dis- cussed later. Using the HI or the S2/S3 ratio, Table 2 suggests the types of products (gas or oil) that will be generated from source rocks ata level of thermal maturation equivalent to R, = 060%, ‘Thermal Maturity of Organic Mater ‘The level of thermal maturation can be roughly estimated from the HI vs. O1 plot described above. Table 3 shows hovr to use the production index (PI) and T,, (0 estimate maturity. In general, Pl and Tha, values less than about 0.1 and 435°C, respectively, indicate immature OM. A Tray greater than 470°C represen the wet-gas zone. The Pl reaches about O4.at the bottom ofthe oil window (beginning of the wet-gas zone) and inereases to 1.0 when the hydrocarbon-generativecapacity of the kerogen has been exhausted. Usually some S1 will remain as adsorbed dry gas, even in highly postmature rocks. ‘The Tr and PI are crude measurements of thermal matu- rity and are partly dependent on other Factors, suchas type of OM, Thus, conclusions regarding thermal maturity should be supported by other geochemical analyses, such as vitrinite reflectance or thermal alteration index (TAI). Table 2, Geochemical Parameters Describing Type of Hydrocarbon Generated HI ‘Type (mg HC/sC, sus3* Gas 0.150 03 Gas and ol 150-300 35 Oil 3004 3+ “hasnesalevl ol harnalmairaion eauvaealoR, = 0%