This document provides an overview of hydrocarbon source rocks. It begins by defining a source rock as a rock capable of generating movable quantities of hydrocarbons. Source rocks are categorized as potential, effective, relic effective, or spent based on their current hydrocarbon generation capabilities. The key factors for evaluating a source rock are the quantity and quality of organic matter it contains, and its thermal maturity level. Quantity is assessed by measuring total organic carbon (TOC) content. Quality depends on the type of kerogen. Maturity is estimated using vitrinite reflectance or pyrolysis analysis. TOC values above 1% for shales or 0.5% for carbonates indicate good hydrocarbon generation potential. Pyrolysis and well logs can also
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Source Rock - TM
This document provides an overview of hydrocarbon source rocks. It begins by defining a source rock as a rock capable of generating movable quantities of hydrocarbons. Source rocks are categorized as potential, effective, relic effective, or spent based on their current hydrocarbon generation capabilities. The key factors for evaluating a source rock are the quantity and quality of organic matter it contains, and its thermal maturity level. Quantity is assessed by measuring total organic carbon (TOC) content. Quality depends on the type of kerogen. Maturity is estimated using vitrinite reflectance or pyrolysis analysis. TOC values above 1% for shales or 0.5% for carbonates indicate good hydrocarbon generation potential. Pyrolysis and well logs can also
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Oleh:
Dr. Ir. Eko Widianto, MT
Jurusan Teknik Perminyakan Fakultas Teknologi Kebumian dan Energi Universitas TRISAKTI
2012 4. Hydrocarbon Source Rock LECTURE MATERIAL 1. INTRODUCTION
2. ORIGIN OF PETROLEUM AND LEVEL OF PETROLEUM INVESTIGATION
3. PLATE TECTONIC AND PETROLEUM SEDIMENTARY BASIN
4. HYDROCARBON SOURCE ROCK
5. RESERVOIR ROCK
6. HYDROCARBON TRAP AND SEAL
7. HYDROCARBON MIGRATION
8. ESTIMATION OF RESERVES AND RESOURCES
9. PETROLEUM GEOLOGY OF INDONESIA Figure: Loss of carbon and related petroleum potential in the sedimentary cycle Demonstrates the chance that any single carbon atom in a carbon dioxide molecule, whether in the atmosphere or hydrosphere, has of being taken in by biotic processes and becoming petroleum. In statistical figures, when 50,000,000 carbon dioxide molecules enter the organic cycle through biosynthesis, only one of the carbon atoms will end up in a petroleum accumulation (Hunt 1972, 1977). This diminution, outlined below, is due to a variety of naturally occurring biological, chemical, and physical processes acting near or below the earth's surface. SOURCE ROCKS BASIC To evaluate a play or prospect in an undrilled area, we must first ask, "Is a source rock present?" But this is usually not enough. After determining that a source rock is present, we also need to know its richness, its quality, and its maturity. This chapter covers all of these topics.
The first factor to be assessed in an exploration play in an area yet to be drilled is whether a source rock is present. If so, then we ask, "How good is it? Will it generate oil or gas? Has it generated hydrocarbons already?" To answer these questions, we must know the basics of what constitutes a source rock, how to classify source rocks, and how to estimate potential. This section provides a background in these fundamentals.
Types of Source Rocks
Definition of Source Rock A source rock is a rock that is capable of generating or that has generated movable quantities of hydrocarbons.
Source rocks can be divided into at least four major categories: Potential Effective Relic effective Spent TYPE DEFINITION Potential source rock Rock which contain organic matter in sufficient quantity to generate and expel hydrocarbons if subjected to increase thermal maturation. Effective source rock Rock which contain organic matter and is presently generating and/or expelling hydrocarbons to form commercial accumulations. Relic effective source rock An effective source rock which has ceased generating and expelling hydrocarbons due to a thermal cooling event such as uplift or erosion before exhausting its organic matter supply. Spent source rock An active source rock which has exhausted its ability to generate and expel hydrocarbons either through lack of sufficient organic matter or due to reaching an over mature state. Characterizing Source Rocks To be a source rock, a rock must have three features: 1. Quantity of Organic matter 2. Quantity capable of yielding moveable hydrocarbon 3. Thermal maturity The first two components are products of the depositional setting. The third is the function of the structural and tectonic history of the province.
Determining the source rock potential The quantity of organic matter is commonly assessed by a measure of the total organic carbon (TOC) contained in the rock. Quality is measured by determining the types of kerogen contained in the organic matter. Thermal maturity is most often estimated by using vitrinite reflectance measurements and data from pyrolysis analysis. The table below shows the most common methods used to determined the potential of the source rock. To determine . Measure Quantity of source rock Total Organic Carbon (TOC), present in the source rock Quality of source rock Proportions of individual kerogen Prevalence of long-chain hydrocarbons Thermal maturity of source rock Vitrinite reflectance Pyrolysis T max Source rock richness is determined by measuring the TOC present in the rock. The two most common techniques of analyzing a rock for TOC are Rock-Eval pyrolysis with TOC and the LECO method. Conventional well logs can also provide information for evaluating interval richness.
This section first discusses what TOC is and then describes these three techniques and the information they yield.
Measuring a Rock's Ability to Generate Hydrocarbons
How do we determine if an interval of strata can be categorized as a source rock? Measuring the total organic carbon (TOC) present in weight percent (wt %) is the most common method for making this determination. A TOC analysis is a screening analysis used to evaluate the overall organic richness of a rock unit. TOC serves as a guideline for assessing the hydrocarbon generating potential of a unit of rock.
Why use TOC Hydrocarbons are 75-95 wt % carbon by molecular weight (Jarvie, 1991) and average 83 wt %. The amount of organic carbon present in a rock is a determining factor in a rock's ability to generate hydrocarbons. Effect of depositional environment Depositional environment controls the amount of organic carbon contained in a rock. Source rocks are generally associated with areas where high organic productivity is combined with:
(1) deposition in poorly oxygenated environments (anoxic to dysaerobic), (2) upwelling, and (3) rapid sedimentation (Chinn, 1991). These processes preserve organic matter.
Average TOCs The table below (from Chinn, 1999) shows average TOC values for different sedimentary rock types. ROCK TYPE TOC VALUE, % Average for all shales 0.8 Average for shale source rocks 2.2 Average for calcareous shale source rocks 1.8 Average for carbonate source rocks 0.7 Average for all source rocks 1.8 The table below gives guidelines for assessing the richness of source rock intervals Generation Potential Wt % TOC, Shales Wt % TOC, Carbonates Poor 0.0 0.5 0.0 0.2 Fair 0.5 1.0 0.2 0.5 Good 1.0 2.0 0.5 2.0 Very Good 2.0 5.0 1.0 2.0 Excellent > 5.0 > 2.0 Using Pyrolysis to Estimate Richness
Pyrolysis is the decomposition of organic matter by heating in the absence of oxygen. Organic geochemists use pyrolysis to measure richness and maturity of potential source rocks. In a pyrolysis analysis, the organic content is pyrolyzed in the absence of oxygen, then combusted. The amount of hydrocarbons and carbon dioxide released is measured. The most widely used pyrolysis technique is Rock-Eval.
The diagram below shows the cycle of analysis and the corresponding recording. In Rock-Eval pyrolysis, a sample is placed in a vessel and is progressively heated to 550C under an inert atmosphere. During the analysis, the hydrocarbons already present in the sample are volatized at a moderate temperature. The amount of hydrocarbons are measured and recorded as a peak known as S1. Next pyrolyzed is the kerogen present in the sample, which generates hydrocarbons and hydrocarbon-like compounds (recorded as the S2 peak), C02 and water (Tissot and Welte, 1984). The CO2 generated is recorded as the S3 peak. Residual carbon is also measured and is recorded as S4.
The table below list the Rock-Eval pyrolysis peaks and explains what they represent. Peak Is a measurement of . Comment S1 Mg HC / g rock The free hydrocarbons present in the sample before the analysis Can be thought of as a residual hydrocarbon phase. When S1 is large relative to S2, an alternative source such as migrated hydrocarbons or contamination should be suspected S2 Mg HC / g rock The volume of hydrocarbons that formed during thermal pyrolysis of the sample Used to estimate the remaining hydrocarbon generating potential of the sample S3 Mg CO2 / g rock The CO2, yield during thermal breakdown of kerogen Most prevalent in calcareous source rock S4 Mg carbon / g rock The residual carbon content of the sample Residual carbon content of sample has little or no potential to generate hydrocarbons due to lack of hydrogen and the chemical structure of the molecule Estimating TOC with pyrolysis
The percent TOC is actually a value that is calculated, not measured directly, using the following formula:
%TOC = [0.082(S1 + S2) + S4]/10
Units are usually given as wt % organic carbon per weight of dry rock (milligrams hydrocarbon per gram of rock).
Using Conventional Well Logs to Estimate Richness
Conventional well logs are useful for estimating source rock richness both qualitatively and quantitatively. Well logs allow a qualitative identification of organic-rich formations and a quantitative analysis of the amount of organic matter. The advantages of using well logs over cuttings are continuous sampling, more accurate depth control, and greater vertical resolution (Herron, 1991).
The use of conventional well logs to predict organic richness of a unit of rock requires calibrating well log intervals to samples measured for TOC using pyrolysis or another suit able measurement technique. Using the calibrated logs, we can extrapolate TOC values to un-calibrated logs to estimate source rock richness over large areas.
Note: Consider changes in depositional environment and maturity when applying these techniques.
Effects of organic matter on well logs The increasing concentration of organic matter in a rock directly affects its properties by lowering density, slowing sonic velocity, increasing radioactivity, raising resistivity, and raising hydrogen and carbon contents. All of these attributes can be measured using density, sonic, neutron, gamma ray, and resistivity logs. The table below (from Herron, 1991) summarizes log responses to organic matter.
Log / Property Response / Value for Organic Matter (OM) Comment Gamma ray (GR) or Uranium (U) High High GR caused by U; can be linear with OM; U not always present Density Low (approx. 1gr/cm3) Similar to pore fluids Neutron High Due to hydrogen in OM Sonic High transit time Estimates vary from 150 to more than 200 micro second/ft Resistivity High May not affect log response unless generated hydrocarbons occupy pores Pulsed neutron High carbon-oxygen ratio Most direct measurement of carbon; needs inorganic correction EVALUATING SOURCE ROCK QUALITY Kerogen Types
Introduction Depositional environment is the dominant factor in determining the types of organic matter found in a rock. Only two types of organic matter are found in rocks: land derived and aquatic algae derived. Heat and pressure convert organic matter into a substance called humin and then into kerogen. Time and temperature convert kerogen into petroleum.
Definition Geochemists (Durand, 1980; Tissot and Welte, 1984) define kerogen as the fraction of sedimentary organic constituent of sedimentary rocks that is insoluble in the usual organic solvents. Kerogens are composed of a variety of organic materials, including algae, pollen, wood, vitrinite, and structureless material. The types of kerogens present in a rock largely control the type of hydrocarbons generated in that rock. Different types of kerogen contain different amounts of hydrogen relative to carbon and oxygen. The hydrogen content of kerogen is the controlling factor for oil vs. gas yields from the primary hydrocarbon- generating reactions.
Kerogen quality The type of kerogen present determines source rock quality. The more oil prone a kerogen, the higher its quality. Four basic types of kerogen are found in sedimentary rocks. A single type or a mixture of types may be present in a source rock. The table below lists and defines these four basic kerogen types. Kerogen Type Predominant Hydrocarbon Potential Amount of Hydrogen Typical Depositional Environment I Oil prone Abundant Lacustrine II Oil and gas prone Moderate Marine III Gas prone Small Terrestrial IV Neither (primarily composed of vitrinite) or inert material None Terrestrial (?) Evaluating Quality Using Rock-Eval HI/OI
Introduction Obviously, the two main elements of hydrocarbons are hydrogen and carbon. Therefore, once we know the amount of organic carbon present in a rock, we then need to know the amount of hydrogen present in order to assess overall source rock quality. The amount of oxygen and hydrogen present in the kerogen defines the kerogen as type I, II, or III and if the rock will be oil or gas prone.
Hydrogen index The hydrogen index (HI) represents the amount of hydrogen relative to the amount of organic carbon present in a sample. The S curve of a Rock-Eval analysis can help us determine the total amount of hydrogen in milligrams of hydrogen to grams of sample according to the following formula:
HI = S2 (mg/g)/%TOC x 100
Oxygen index The oxygen index (OI) represents the amount of oxygen relative to the amount of organic carbon present in a sample. The S curve of a Rock-Eval analysis can help us determine the total amount of oxygen present in a sample according to the following formula: OI = S3 (mg/g)/%TOC x 100 Determining kerogen quality
The type of kerogen pre sent in a rock determines its quality. Type I kerogen is the highest quality; type III is the lowest. Type I has the highest hydrogen content; type III, the lowest. To determine the kerogen type present in a source rock, plot the hydrogen and oxygen indices on a modified Van Krevlen diagram (below).
Typical graphic formats used to determine kerogen types from analytical data: Hl and Ol pyrolysis plot Using Pyrolysis Gas Chromatography to Assess Quality
What is Py-GC? Pyrolysis gas chromatography (Py-GC) is anhydrous thermal decomposition of a material that leads to the conversion of kerogen to hydrocarbon compounds. Py-GC can be conduct ed on whole rock or isolated kerogen samples to obtain a visual signature or fingerprint of the organic material present.
How to read gas chromatograms Gas chromatography generally is a qualitative tool. It is not typically used as a quantitative measurement of hydrocarbon molecules. However, the patterns generated in the chromatograms can help us determine if a source rock will be oil or gas prone. The X-axis of a gas chromatogram is retention time, and the Y-axis is the relative quantity of each compound. Each spike in the chromatogram represents a particular hydrocarbon compound, beginning with lowest number of carbon atoms in the compound on the left and going to higher chains of carbons to the right. The height of the spike represents the relative abundance of the compound pyrolized from the samples kerogen.
Interpreting gas chromatograms A gas chromatogram is evaluated qualitatively to determine the potential of a rock to generate oil vs. gas. The table below shows how chromatograms for oil- vs. gas-prone rocks are evaluated. Chromatograms of oil-prone rock Chromatograms of gas-prone rock Dominated by long-chain carbon compounds (greater than C10) Dominated by short-chain carbon compounds from C1 C4 Contain carbon compounds up to C25 or greater Contain very few carbon compounds above C10 Typical gas chromatogram examples for types I, II, and III kerogen are shown below. EVALUATING SOURCE ROCK MATURITY Once the two questions Is a source rock present? and What type of hydrocarbon will it generate? have been answered to our satisfaction, we must ask, Has it generated hydrocarbon?. In other words, what is its present-day maturity?
Maturation
Introduction The chemistry of organic matter contained within a sedimentary rock changes over time, reflecting its temperature and burial history. This change or maturation is measured and can be combined with quality and richness data to gauge the amount of hydrocarbon generated by the organic matter. The present-day maturity level is the product of a number of variables, such as tectonic setting, burial history and thermal history A number of variables such as paleolatitude, pressure, fluid flow, rock matrix chemistry, and pore fluid chemistry can affect the thermal history and thus a rocks rate of maturation.
Transformation rate The rate at which hydrocarbons are generated from organic matter is called the transformation rate. Using source rock maturity, we can estimate the transformation rate. Different kerogen types (1) generate hydrocarbons at different maturity levels and (2) have different transformation rates. Maturity measurements can be made on several different components of a rock like vitrinite, kerogen, spores, apatite grains, and biomarkers; each has its own relationship to the kerogen transformation rate. Tmax
Introduction Tmax is the temperature at which the maximum rate of hydrocarbon generation occurs in a kerogen sample during pyrolysis analysis. The S2 peak represents the rate of hydrocarbon generation (the area under the curve represents the amount). The temperature at the time the S2 peak is recorded during pyrolysis is Tmax, given in C. The diagram below shows output from a pyrolysis analysis and when Tmax is recorded. Maturation trends plotted from pyrolysis data. On this well-profile plot of Tertiary, West Africa core samples, an increase in productivity index (PI) and Tmax accompanies increased depth of burial
Interpreting Tmax We can use the general guidelines for maturation levels given below for Rock-Eval pyrolysis Tmax for types II and III kerogens. Different pyrolysis techniques have different cutoffs for pyrolysis oil and gas generation zone boundaries. Pyrolysis Tmax can be significantly different for type I kerogen (Tissot et al., 1987) or kerogen containing high sulfur concentration and is not a reliable indicator of maturity for these kerogen types. Hydrocarbon Generation Zone Rock-Eval Pyrolysis Tmax, o C Immature < 435 Oil (from type II kerogen) 435 455 Oil (from type III kerogen) 435 465 Gas (from type II kerogen) > 455 Gas (from type III kerogen) > 465 Vitrinite Reflectance
Introduction Vitrinite reflectance is a measure of the percentage of incident light reflected from the surface of vitrinite particles in a sedimentary rock. It is referred to as %Ro Results are often presented as a mean Ro value based on all vitrinite particles measured in an individual sample.
Connection between vitrinite and kerogen The maturation of vitrinite is a kinetic process. The relationship between %Ro and hydrocarbon generation is dependent on the chemistry of the vitrinite as well as the chemistry of the kerogen.
Oil and gas zone Oil and gas zone boundaries can be established using vitrinite reflectance data. The boundaries are approximate and vary according to kerogen type. The figure below shows the approximate boundaries for kerogen types I, II, and III. Timetemperature relationships and mixing of various sources of organic matter may alter these boundaries. Recognizing good data An excellent way to recognize high-quality reflectance data is to plot it in a histogram. We can have high confidence in the data when a single mode in the distribution curve is tightly clustered about a mean value. The histogram below is a good example.
Sample with reworked vitrinite
The bimodal distribution shown in the histogram below represents an indigenous and a reworked population of vitrinite measured in one sample. The reworked population would have been eroded from a more mature provenance and deposited with the indigenous organic matter of this sample. Hydrogen Index (HI)
Introduction Gross trends of hydrogen indices (HI) can be used as a maturation indicator. The hydrogen index is calculated from Rock-Eval data using the following formula:
HI = S2 (mg/g)/%TOC x 100 How to apply HI Hydrocarbon generation zones can be indicated in the HI data for a uniform source section when HI decreases with depth. Inconsistencies due to changes in organic facies or the chemistry of the source rock can produce shifts in the HI data which are not indicative of maturation trends. Therefore, be sure the source is of uniform character when applying this concept. The figure below shows a decreasing HI trend for a source rock beginning to generate hydrocarbons at a depth of approximately 2200 m. Production Index (PI)
Introduction Maturity of a homogeneous source section can be accessed from the production index (PT). PI is calculated from Rock-Eval data:
PI = S1/(S1 + S2) How to apply PI PI increases continuously through the oil window up to a value of 0.50. The following cutoffs can generally be applied. Production Index Generation Zone < 0.10 Immature 0.10 0.30 Oil Generation > 0.30 Gas generation / oil cracking Relationships Between Maturity and Hydrocarbon Generation
Introduction
Different types of kerogens convert to hydrocarbons at different rates, and they yield different quantities of various hydrocarbon phases. Therefore, one standard relationship between a measured maturity parameter and hydrocarbon generation does not exist. Values such as 0.6% Ro are generally associated with the onset of oil generation or indicate the top of the oil window. However, this generality applies only if a source rock is com posed of pure type II organic matter (marine kerogen). This section reviews some of the relationships between maturation indicators and hydrocarbon generation from standard kerogen types.
Kerogen Type and Hydrocarbon Generation
Kerogen consists of many fractions, each converting to hydrocarbons at a specified rate. This rate of conversion to hydrocarbons is defined by a first-order rate equation known as the Arrhenius law:
dx / dt = - kx With : k = A exp (-E/RT) A is the pre exponential factor (s -1 ) E is the apparent activation energy (kcal/mol) R is the gas constant (0.001987 kcal/mol) T is the temperature ( o K)
These are generally referred to as kinetic parameters. They can be measured using various pyrolysis techniques and are different for each distinct kerogen analyzed.
Hydrocarbon generation depth and yield The depth of hydrocarbon generation and the yield of individual hydrocarbon phases are primarily a function of the kinetics of the kerogen - hydrocarbon conversion. Burial history and catalytic effects, due to source rock matrix chemistry; affect the rate of generation, although these effects are secondary to the kinetic effects. Comparison of Kerogen Types
The table below shows examples of the relationships between hydrocarbon generation zones, maturity, and transformation ratio for standard types II and III kerogens, based on a specific burial and thermal history model. The most significant difference is in the depth to the onset of oil generation, where 1000 m separates the top of the oil windows of these two kerogen types.
Hydrocarbon Generation Zone Vitrinite Reflectance, %Ro Transformation Ratio, % Present-day Depth, m Type II Type III Type II Type III Type II Type III Onset Oil 0.55 0.85 5 12 2200 3200 Onset peak rate generation 0.65 1.00 17 31 2600 3500 Onset gas/cracking liquids 0.95 1.35 88 64 3400 4050 Maturation indicators as related to bitumen generated from different kerogen types