Characterization of hydrocarbon

generation and expulsion via the

e_GENESI
Lea Di Paolo (Geolab)

External Research Partners

Christian Albrechts University of Kiel

(Germany)

Outline
Introduction
Expulsion
Standard methodologies

e_GENESI device
Sample characteristics
Main activities
Step-wise experiments

Sample set
Comparison with standard methodologies (CSVP)
Generation and expulsion profiles
Compression/expansion of the source rock
Expulsion indicators
Porosity

Summary
Ongoing project

Expulsion definition and its key role in hydrocarbon accumulation

Processes leading to accumulation of oil and gas
Exploration geochemistry

Expulsion: movement of the newly formed oil molecules away

from the kerogen particle through relatively impermeable finegrained source rocks.

IFE report 2013 exp exp project

Poor
Poor understood
understood

Only part of the oil and gas generated

by the source rock is expelled, the rest
is retained within the kerogen
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Expulsion & Migration

Diffusion within the kerogen
network
adsorption/desorption of
hydrocarbons by kerogen

ongoing
subsidence
(pressure
increase)

Desorption of hc from kerogen

into pore wall and Aggregation
from the pore wall into the pore
space of the source rock
Fluid Flow within the source
rock (pressure-driven)
micro-/macro-fractures &
secondary porosity
Stockhausen PhD thesis

The interactions of this

effects and the impact
to
expulsion and primary
migration is still
unknown.
They are influenced by
fracturing, adsorption
and desorption by
kerogen,
smectite to illite
transformation (release
of water, increase of
pore pressure)

State of the Art - External knowledge and technology contest

Experimental:
experiments on crushed source rocks, no information on the effect of the rock
texture on the expulsion and no application of an uni-axial (lithostatic) pressure.
experiments on intact source rocks, the diameter of the source rock specimen used
was very small compared to its thickness.
Open system Pyrolysis
(RockEval)
(used by Eni)

Closed System
Pyrolysis (MSSV)
(used by Eni)

Helium Flow
Generated HCs

Source Rock Fragments

no expulsion
no secondary
cracking

Generated HCs

no expulsion
Source Rock Fragments

Numerical:
based on theoretical assumptions (no consensus on primary migration process)
lack of primary migration experimental calibration.

System Requirements for Near-Natural Simulation

A laboratory simulation of the natural
processes of generation, expulsion and
primary migration has to cover the maximum
of oil generation, equivalent to a burial depth
of ~3000 m at a normal geothermal gradient
of 33 C/km that requires:
300 bar max pore pressure
(hydrostatic) (Sahay, 1999)
900 bar max lithostatic pressure
(Sahay, 1999)
up to 360C HC generation
temperatures (Lewan, 1997;
Lewan et al., 1979)

eni_GENeration and Expulsion Simulator: e_GENESI

Near-nature simulation of expulsion by:
use of an intact source rock disc and of an
artificial reservoir
control of temperature (up to 350C)
control of hydrostatic (up to 300-500 bar)
and lithostatic pressures (up to 900-1500
bar)
sampling oil and gas in semi-continuous way
sampling source rock plugs at different step
of thermal maturation
open system pyrolysis (prevents secondary
reactions)
hydrous pyrolysis:
support of migration
hydrogen donor

Controlling
unit
HP-unit

Hydraulic
unit

technology
Cell

Sampling
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Sample Assembly and Flow Directions

The sample disc is surrounded by
an artificial reservoir (sinter filter
with 50 % porosity).

outlet

inlet

To prevent lateral movement of the

rock, the filter-rock assembly is
installed in a protection tube.
Expelled products accumulated
within the pore space of the
artificial reservoir.
Products were flushed out by a
directed flow.

artificial
reservoir

rock
disc

Possible Simulation Scenarios

~2000 m ~2500 m ~3000 m
Overburden
pressure
Pore
pressure
Pyrolysis
temperature
duration

600 bar

750 bar

900 bar

200 bar

250 bar

300 bar

300 C

330 C

360 C

72 h

72 h

120 h

Possibility to simulate a
variety of geological
processes (subsidence & uplift
with different rates, isobar &
isothermal conditions,
different heating and cooling
rates, etc.)

Catagenesis simulation by a
step-wise experiments

Subsidence simulation by a
ramp experiments

Simulation of uplift

Pressure controlled expulsion

experiments

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Samples
The e_GENESI device is designed for samples with a diameter of 50 mm ( 4 mm).
Processing of samples with smaller diameter involves the risk of inaccurate pressure
application and incomparable expulsion behavior.
The ideal sample quantity is based upon the OM content of the sample:
For Type-I and II kerogen: Between 5 to 7 g
TOC within the cell (~ 60 g for a sample with 10
% TOC).
For Type-III kerogen: Between 8 to 12 g TOC
within the cell (~ 20 g for a sample with 50 %
TOC).

Immature Type I/II Source Rock - Toarcian Posidonia Shale

immature fresh source rock from active quarry

large volume sampling
multiple plugs drilled from a single rock layer

Barnett
Shale
(very
sturdy)
17.0 mm

15.1 mm

after

10.9 mm

after

16.5 mm

before

Posidonia
Shale
(ductile)

before

Lithostatic Pressure Response

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Main Activities
Kiel University:
e_GENESI experiments on
different source rocks
Analysis of the expelled
hydrocarbons
Eni laboratories (source rock
samples characterization):
Optical analysis of organic
matter (GEOLAB)
RAMAN and FTIR
spectroscopy (GEOLAB and
DOW-R&D)
SEM-microscopy analysis
(DOW-R&D)
Numerical source rock model
calibration (RIGE)

Expelled HCs
(

Optical analysis

Rock Eval Pyrolisis

HR-SEM

Ro%=0.2

Ro%=0.5
Oil
Gas
Ro%=1.3

FTIR spectroscopy

ATR-FTIR and Raman

spectroscopy

1.4 Ro%
Ro%=2.0

Vitrinite
Reflectance (VRo
%)

Alteration colours
of palinomorphs
(SCI and TAI)

0.29 Ro%

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Step-wise experiments - Expulsion profiles and product yields

~1.3%Rocalc

CO2 gases (mg/g

TOC)

~0.9%Rocalc

C1-C5 gases (mg/g TOC)

Extract yield (mg/g TOC)

~0.7%Rocalc

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Source Rock Type & Lithology

Kerogen
type

Type-I

Type-I/II
&
Type-II

Formation

Note

Foulden Maar (early Miocene)

freshwater diatomite deposit

(very ductile)

no diagenetic overprint (limitations in

comparability to the other samples)

Green River (early through middle

Eocene)

lacustrine lamosite,
limestone/dolostone (brittle)

high grade of cementation (authigenic

carbonate & silica)

Posidonia Shale (lower Jurassic)

bituminous black shale, argillite

(ductile)

hybrid-kerogen type-I/II (increased

lacustrine influence)

Barnett Shale (Paleozoic - late

Mississippian)

siliceous mudstone (very sturdy)

high grate of silification

Malm Limestone (Jurassic)

bituminous marls (alternating

carbonate & OM rich clay layers)
(sturdy)

Besano Fm. - Dolomite (middle

Triassic)

interlayered dolomites, dolomitic

marls and black shales (brittle)

Tettegras Fm. - Coal (lower

Carboniferous)

liptinite-rich coals (ductile)

high liquid hydrocarbon potential

Inden Member lignite (latest

Miocene age)

Lignite (very ductile)

lower Rhine Basin (Aachen-Cologne

lignite mining district)

Type-IIS

Type-III

Lithology

iron-limited environment (reducing) &

early diagenetic sulfur reactions
high organic sulfur content

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Rock Eval Data

unusual low
HI-value due
to missing
diagenetic
overprint

excellent source
rock quality for
type-I and type-II
kerogens
still good source
rock quality for
Tettegras Fm.
Quality of Inden
lignite in the
excepted ranch.

17

Extract yield: e_GENESI vs CSVP experiments

Lower extract yields in case of CSVP
polymerization & condensation, formation of
pyrobitumen instead of free hydrocarbons
Type-IIS: most extract & largest difference to CSVP
early generation increases polymerization
Type-I and I/II: high/moderate extract yields and variable
difference to CSVP
reduced polymerization due to late generation
reduced expulsion by lithology (high rate of
cementation)
Type-III: lowest extract yields and lowest difference to CSVP
polymerization of bitumen, retained within kerogen
network

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Maturity assessment of artificially matured samples by Rock Eval

e_GENESI vs CSVP
CSVP of type-I and type-II shows values close to each
other in a small Tmax-area between 446 C and 455 C
Different Tmax values from e_GENESI experiments:
type I/II< type II/IIS < type III
Tmax-values of CSVP-experiments represent rather the
thermal resistance of the generated pyrobitumen than of
the residual kerogen.
In contrast, Tmax-values of the e_GENESI experiments
correspond to the residual kerogen, as it is not masked by
pyrobitumen.
Early removal of generated products has great impact
onto the maturity assessment, in particular
influencing the Tmax value in dependence of the
kerogen type.

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Generation Expulsion Profiles

Foulden Maar

Type I
Green River

Type I/II

Posidonia Shale

Type II

Barnett Shale

Malmian Limest.

Type IIS
Besano Fm.

Tettegras Fm.

Type III
Lignite

In situ bitumen

Type IIS
Malmian L.

Type III
Tettegras Fm

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CO2 gases (mg/g TOC)

extreme early onset of

generation and expulsion
(~2km) without larger
retention (type III)

Type II
Barnett Shale

C1-C5 gases (mg/g TOC)

no generation, only
expulsion of in-situ bitumen
(in line with literature)

Extract yield (mg/g TOC)

Type I
Green River

Liquid products: Generation expulsion profiles

decreasing generation and

expulsion, maximum during the
first stage (III)

Type IIS
Malmian L.

Type III
Tettegras Fm

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CO2 gases (mg/g TOC)

high generation & expulsion rate

during the mid-stage & the last
stage of the experiment (II/IIS)

Type II
Barnett Shale

C1-C5 gases (mg/g TOC)

increasing generation and

expulsion maximum during the
last stage (I-I/II)

Extract yield (mg/g TOC)

Type I
Green River

Gaseous Products: Generation expulsion profiles

Type I
Green River

Type III --- lowest HC-gas

generation & expulsion within the
mid-stage

Type IIS
Malmian L.

Type III
Tettegras Fm

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CO2 gases (mg/g TOC)

Type I and II --- increasing HCgas expulsion during the

experiment

Type II
Barnett Shale

C1-C5 gases (mg/g TOC)

delayed HC-gas expulsion within

the generation stages

Extract yield (mg/g TOC)

gas expulsion simultaneously

with liquid expulsion

Bimodal peak

Type IIS
Malmian L.

Type III
Tettegras Fm

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CO2 gases (mg/g TOC)

Type II
Barnett Shale

C1-C5 gases (mg/g TOC)

Gaseous products: bimodal laststage peak

Primary gas formation by
kerogen decomposition
oil-to-gas cracking at
higher temperatures

Extract yield (mg/g TOC)

Liquid products: Bimodal midstage peak

pore system collapse due
to volume loss by OM
conversion and expulsion
secondary cracking
processes of restrained
products and subsequent
expulsion could contribute
to the second expulsion
peak.

Type I
Green River

CO2: Generation expulsion profiles

Type I
Green River

main CO2 release during the

first stage.

Type IIS
Malmian L.

Type III
Tettegras Fm

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CO2 gases (mg/g TOC)

Type II
Barnett Shale

C1-C5 gases (mg/g TOC)

Type IIS - amount of expelled

CO2 increased with ongoing
subsidence.
source of CO2:
decomposition
reactions of
carbonate and
dolomite

Extract yield (mg/g TOC)

minor CO2 peaks during the

2nd and 3rd stage, coupled to
liquid expulsion

Generation vs Generation+Expulsion timing

Tettegras Fm.

COMPARISON TOTAL YIELD

ENI DATA VS KIEL DATA
35
30

Generation-Expulsion
delayed in comparison to
the generated
hydrocarbons in second
and third steps

25
20
ROCK EVAL TOTAL YIELD (mg/g TOC)

15

TOTAL YIELD (mg/g TOC ) - ENI

TOTAL YIELD (mg/g TOC ) - KJEL
TOTAL YIELD (mg/g TOC ) - KJEL

10
5
0

Time (h)

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Compression/Expansion of the source rock

Compression of the rock sample shows a
long-time trend, reflecting the applied
lithostatic pressure.
Subtraction of the long time trend from
the compression data reveals small scale
movements in m-scale:
Relaxation-compaction sequences,
indicating generation and
expulsion of OM.
First expansion-compression sequences
are linked to CO2 expulsion.
The two last sequences reflect
generation and expulsion of liquid (1st)
and gaseous (2nd) products.

Pr/n-C17-Ratio as Expulsion Indicator

GENERATION PHASE
Retention, as postulated in previous
studies, is not the main control on
Pr/nC17
Strong retention would raise the ratio
and not lower it!
Generation and expulsion/primary
migration is a simultaneous process
Useful expulsion indicator!

Increase of the ratio at the early stage of expulsion due to release of

pristane, possibly with retention effect.
Decrease after reaching a maximum is clearly due to a favored generation
and expulsion of n-C17.

Porosity Before and After the e_GENESI experiment

A porosity increase is noticeable for

samples with high TOC conversion.
Reduced expulsion efficiency caused
by the competent lithology and the
high grade of silification resulted in
lowered porosity for the Barnett
Shale.
Secondary reactions caused solid
bitumen formation, reducing the pore
space available.
80% TOC conv.

40% TOC conv.

Eni internal activities on artificially matured samples

GEOLAB-CHIF Research Collaboration
ATR-FTIR and RAMAN spectroscopy
maturity parameters on both artificially and
naturally matured samples

Bonoldi et al., 2016 (Vibrational spectroscopy)

Webinar - Application of the High Resolution Scanning
Electron Microscopy (HRSEM) in Barnett Shale
characterization
Reference - E. Di Paola (CHIF DOW-R&D)
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Summary - 1
The e_GENESI represents a unique method to simulate the generation and
expulsion of oil and gas under nature near pressure conditions with an intact
rock specimen.
A variety of data is delivered by an e_GENESI experiment, including
expansion-compression data, gas yields and extract quantities.
Pressure and temperature regimes are freely programmable, opening the
possibility to simulate a variety of geological processes.

Summary - 2
Generation & Expulsion efficiency depends on the nature of the organic matter
and of the lithology.
Sturdy and/or low-permeable lithology reduces expulsion efficiency.
Differences in the generation profiles were caused by kerogen type and by the
lithology of the rock sample.
Expulsion profiles do not always meet expectations or textbook knowledge!
Bitumen, HC-gas and CO2 composition in dependence of simulated depth shows
unique pattern for every kerogen type.
Generation dependent ratios are still applicable as expulsion indicators (e.g.
Pr/n-C17).

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Ongoing project
Increase of data density concerning lithotypes and kerogen types:
Posidonia Shale
Vaca Muerta Fm.
Norwegian coal sample
Bonarelli Level
Ramp experiments different heating rates

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