ROCK-EVAL PYROLYSIS

Lab Assignment

HAMZA MASOOD
MSC FINAL (H1514018)
-
Introduction
Introduction The well-known Rock-Eval pyrolysis method (Espitalie et al., 1977, 1980, 1985/86)
is now widely used for the standard characterization of sedimentary organic matter in petroleum
exploration.

For a whole-rock sample, the pyrolysis recording of hydrocarbon generation as a function of

temperature usually shows two well-defined peaks. Espitalié et al., (1977) stated that the first peak
(S1) represents the free and adsorbed hydrocarbons already present, vaporized at 300°C, and that
the second peak (S2) represents the hydrocarbons generated directly from the kerogen, by thermal
cracking at 30o-500°C.According to them, SI is a measure of the bitumen content and S2 is a
measure of the insoluble kerogen content, expressed in kg/ton of rock. The ratioS1/ (S1 + S2)
(production index, PI) is an evaluation of the transformation ratio of kerogen into oil (in the
absence of migration). The temperature Tmax recorded at the maximum of hydrocarbon generation
during pyrolysis, is used in kerogen maturation rank evaluation. The hydrogen index, HI
(S2/organic car-bon), is used for characterizing the type and origin of the kerogen.

Definition of pyrolysis

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.

Principle of Rock-Eval pyrolysis

The oven was initially kept isothermally at 300℃ for 3minutes during which time the free
hydrocarbons are volatilized and the S1 peak is measured by the Flame Ionization Detector (FID).
Pyrolysis of organic matter was later performed at 300-600℃ with a temperature rise of 20 21. 25
℃/ min. This is the phase of volatilization of the higher carbon number hydrocarbons compounds
(>C40) as well as the cracking of non -volatile organic matter. The hydrocarbons released from
this thermal cracking are measured as the S2 peak (by FID). The temperature at which S2 reaches
its maximum depends on the nature and thermal maturity of the kerogen and this is measured as
Tmax. The CO2 produced from kerogen cracking is trapped in the 300 - 390℃ range. The trap is
heated, and CO2 is released and detected on a Thermal Conductivity Detector (TCD) or IR detector
during the cooling of the Pyrolysis oven (S3 peak). The HI was determined as the yield of reduced
products of pyrolysis (S2) relative to the TOC (mg HC/g TOC) and OI is the yield of the oxygen
and bound organic carbon (S3).

Parameters Registered By Pyrolysis Rock-Eval

S1 = the amount of free hydrocarbons (gas and oil) in the sample (in milligrams of hydrocarbon
per gram of rock). If S1 >1 mg/g, it may be indicative of an oil show. S1 normally increases with
depth. Contamination of samples by drilling fluids and mud can give an abnormally high value for
S1.

S2 = the amount of hydrocarbons generated through thermal cracking of nonvolatile organic

matter. S2 is an indication of the quantity of hydrocarbons that the rock has the potential of
producing should burial and maturation continue.

S3 = the amount of CO2 (in milligrams CO2 per gram of rock) produced during pyrolysis of
kerogen. S3 is an indication of the amount of oxygen in the kerogen and is used to calculate the
oxygen index (see below). Contamination of the samples should be suspected if abnormally high
S3 values are obtained. High concentrations of carbonates that break down at lower temperatures
than 390°C will also cause higher S3 values than expected.

Tmax = the temperature at which the maximum release of hydrocarbons from cracking of kerogen
occurs during pyrolysis (top of S2peak). Tmax is an indication of the stage of maturation of the
organic matter.

HI = hydrogen index (HI = [100 x S2]/TOC). HI is a parameter used to characterize the origin of
organic matter. Marine organisms and algae, in general, are composed of lipid- and protein-rich
organic matter, where the ratio of H to C is higher than in the carbohydrate-rich constituents of
land plants. HI typically ranges from ~100 to 600 in geological samples.

OI = oxygen index (OI = [100 x S3]/TOC). OI is a parameter that correlates with the ratio of O to
C, which is high for polysacharride-rich remains of land plants and inert organic material (residual
organic matter) encountered as background in marine sediments. OI values range from near 0 to
~150.
PI = Production index (PI = S1/ [S1 + S2]). PI is used to characterize the evolution level of the
organic matter.

PC = pyrolyzable carbon (PC = 0.083 x (S1 + S2)). PC corresponds to carbon content of

hydrocarbons volatilized and pyrolyzed during the analysis.
Areas of application of Rock-Eval pyrolysis

Successful petroleum exploration relies on detailed analysis of the petroleum system in a given
area. Identification of potential source rocks, their maturity and kinetic parameters, and their
regional distribution are best accomplished by rapid screening of rock samples (cores and/or
cuttings) using the Rock-Eval apparatus. The technique has been routinely used for about fifteen
years and has become a standard tool for hydrocarbon exploration. We will describe how the new
functions of the latest version of Rock-Eval (Rock-Eval 6) have expanded applications of the
method in petroleum geoscience. Examples of new applications are illustrated for source rock
characterization, reservoir geochemistry, and environmental studies, including quantification.

1. Exploration Areas
Successful petroleum exploration relies on detailed analysis of the petroleum system in a
given area. Identification of potential source rocks, their maturity and kinetic parameters,
and their regional distribution are best accomplished by rapid screening of rock samples
(cores and/or cuttings) using the Rock-Eval apparatus. The technique has been routinely
used for about fifteen years and has become a standard tool for hydrocarbon exploration.

Figure 1 Source rock evaluation using Rock eval pyrolysis data

2. Production Areas
Geochemistry of reservoirs is an area of growing interest with remarkable economic
importance because it can be used to evaluate reservoir continuity during field appraisal,
to identify non- productive reservoir zones, and to analyze commingled oils for production
allocation calculations (e.g. Kaufman, 1990; England and Cubitt, 1995). The Rock-Eval
method has already been successfully applied in reservoir geochemistry, especially for the
detection of tar-mats and for the prediction of oil API gravities (Trabelsi et al., 1994). For
reservoir geochemistry, the main advantage of Rock-Eval 6 is its capability to perform both
pyrolysis and oxidation of the sample up to 850°C at various rates. Figure IV-3 is an
example of Rock-Eval 6 results for four different reservoir rocks: three sandstones and one
carbonate. The first sample represents a conventional oil accumulation that produces a
large S1 peak and a smaller S2 peak. Almost no CO and CO2 are generated during
oxidation. The second sample shows a small S1 peak, a bimodal S2 peak (small S2a and
large S2b) and significant amounts of CO and CO2 released during oxidation. This sample
is from a conventional tar-mat, i.e. a reservoir rock accumulated with crude oil enriched in
resins and asphaltenes. For the last sandstone reservoir, we still observe the S1, S2a and
S2b peaks but we also observe an important CO2 peak produced during oxidation at high
temperature (near 800°C). Since we also observed this peak in the rock sample after
decarbonatation, it cannot be caused by carbonate decomposition of minerals in the
sandstone matrix. This peak corresponds to the combustion of refractory material
associated with pyrobitumen in the sample. Therefore, it seems possible, from the
comparison of the oxidation curves of two tar-mat levels, to distinguish a conventional tar-
mat deposited in the reservoir from a pyrobitumen produced by in-place secondary
cracking of an oil accumulation. This distinction is very important since it can guide
exploration and production strategies in oil fields with tar-mats. The carbonate reservoir
sample shows the same pattern in the FID trace as that observed for the conventional tar-
mat in the sandstone reservoir. This is typical of the large amounts of resins and asphaltenes
present in the rock. During the oxidation phase of the sample, the strong CO2 production
at about 500°C and the CO production correspond to the residual organic carbon, whereas
the very large amount of CO2 produced at higher temperature corresponds to the
decomposition of the carbonate matrix.
3. Environmental Areas
Due to its economic, environmental and industrial importance, the characterization of soils
contaminated by hydrocarbons is another area where research is very active. Rock-Eval 6
expands the application of pyrolysis methodology to oil-contaminated sites by making it
possible to start the analysis at low temperature (100°C). Furthermore, heating rates can be
adjusted so as to release the different petroleum cuts (e.g., gasoline, diesel oil, heavy oils,
lubricant oils, and gas plant distillation residues). In this application (called Pollut-Eval),
the vaporized hydrocarbons are identified by the FID and the signal is integrated for full
quantification. A complete carbon mass balance is then carried out through oxidation of
the residue and continuous quantification of CO2 by the infrared detectors. For these types
of studies, the apparatus is equipped with a cooled auto sampler that reduces the loss of
light compounds. The equipment thus provides the parameters needed to characterize a
contaminated site: what pollutant, how much and where? Due to the short duration of the
analysis (30 min), the time needed to evaluate the extent of a contaminated site is drastically
decreased compared to routine techniques that involve the extraction of the pollutant prior
to its analysis by chromatography, infrared or chromatography-mass spectrometry.
Furthermore, when applied on site, the measurements can be used to optimize the drilling
program (Ducreux et al., 1997). Rock-Eval 6 data can be correlated to standard
environmental data such as infrared response. They are also complementary to infrared or
gas chromatographic analyses because they allow rapid screening of a large number of
samples, thus helping to identify the samples that are worthy of additional study. An
example of the application of Rock-Eval 6 data for two industrial sites is presented in figure
IV-5. The upper part of the figure shows contamination by diesel oil and polyaromatic
hydrocarbons in a soil near an old gas plant. The FID trace indicates two main peaks
corresponding to the mixture of these hydrocarbons and the CO and CO2 traces during
oxidation are characteristic of the combustion of the heavy residue accompanying these
products in the pollution. The second example is taken from contaminated soil near a
service station. Light gasoline-range compounds are released early during pyrolysis and no
significant amounts of CO and CO2 are recorded during oxidation.
Conclusion

The new Rock-Eval 6 pyroanalyzer marks an important step in the development of programmed
pyrolysis systems. This apparatus provides new functionalities and parameters that expand
applications of the technique in petroleum geoscience. Problems related to the older Rock-Eval
systems have been ameliorated. The major improvements and their scientific impact can be
summarized as follows:

➢ Impact on source rocks facies analysis

➢ Impact on the knowledge of source rocks preservation conditions
➢ Improved measurements of TOC and Tmax
➢ Better analysis of type III source rocks
➢ Better analysis of heavy bitumen in reservoirs (tar-mat studies)
➢ Better characterization of coals 40

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