Maturation and expulsion

Department of Petroleum Technology, University of Karachi

 Conversion of Kerogene to Oil and Gas

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 Maturation and expulsion
• With increasing burial by later sediments and increase in
temperature, the kerogen within the rock begins to break
down.

• This thermal degradation or cracking releases shorter

chain hydrocarbons from the original large and complex
molecules found in the kerogen.

• The hydrocarbons generated from the source rock are

expelled, along with other pore fluids, due to the
continuing effects of compaction and start moving
upwards towards the surface, a process known as
migration.

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 Oil and Gas Conversion

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 Rock Pyrolysis
• S1 = the amount of free
hydrocarbons (gas and oil)
in the sample (in milligrams
of hydrocarbon per gram of
rock).

•S2 = the amount of

hydrocarbons generated
through thermal cracking of
nonvolatile organic matter.

S3 = the amount of CO2 (in

milligrams CO2 per gram of
rock) produced during pyrolysis
of kerogen.

Oxygen bearing volatile

compounds are passed to a
separate detector, which
produces as S3 response.

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 Rock Pyrolysis

• Espitalie developed a standard procedure for the pyrolysis of

rock samples known as ROCK-EVAL PYROLYSIS.

• Method: About 100 mg finely ground rock sample is placed into

a furnace at 250 degree C in an inert atmosphere than raised to
a temperature of 550 degree C.

• The amount of Hydrocarbon products evolved is recorded by a

Flame Ionization Detector (FID) as a function of time.

• Three Peaks are typically, Known as S1, S2 and S3 peaks are

evolved and recorded.

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 Example of Rock Eval trace. HC = hydrocarbon
• 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 is an indication of the quantity of hydrocarbons

that the rock has the potential of producing.

The burial and maturation should continue at this

stage.
This parameter normally decreases with burial
depths >1 km.
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 Example of Rock Eval trace. HC = hydrocarbon
• S3 = the amount of CO2 (in milligrams CO2 per gram of
rock) produced during pyrolysis of kerogen.

• Oxygen bearing volatile compounds are passed to a

separate detector, which produces as S3 response.

• S3 is an indication of the amount of oxygen in the kerogen

and is used to calculate the oxygen index.

• Contamination of the samples should be suspected if

abnormally high S3 values are obtained.

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Hydrogen index/oxygen index plot from Rock Eval pyrolysis
data. TOC
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.

. PC = pyrolyzable carbon (PC = 0.083

x [S1 + S2]).
PC corresponds to carbon content of
hydrocarbons volatilized and
pyrolyzed during the analysis.

Department of Petroleum Technology, University of Karachi

Hydrogen index/oxygen index plot from Rock Eval pyrolysis
data. TOC
. 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.
PI = production index

(PI = S1/[S1 + S2]).

PI is used to characterize the evolution
level of the organic matter.

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 EXPULSION EFFICIENCY

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 PGI and PEE
Mackenzie and Quigley (1988) has classified source rocks into
three end member classes on the basis of initial kerogene
concentration and kerogene type.
These parameters determine the timing and composition of
petroleum expelled.

PGI : (Petroleum generation Index)

is the fraction of petroleum prone organic matter that has been
transformed into petroleum, and is thus a measure of source
maturity.

PEE: (Petroleum expulsion efficiency)

is the fraction of petroleum fluids formed in the source rock that
have been expelled

Department of Petroleum Technology, University of Karachi

 PGI and PEE
• Class I:
Predominantly Labile Kerogen at concentration of 10Kg/ton and generation
start at about 100 degree C.
This rapidly saturates the source rock and between 120-150 degree C 60%-90%
is expelled as oil with dissolved gas.
The remaining fluid crack to gas at higher temperature and expelled as gas.

• Class II:
This is linear version of Class I with initial Keregen concentration < 5Kg/ton.
Expulsion is inefficient up to 150 degree C because insufficient oil-rich
petroleum generated.
Petroleum is expelled mainly as gas condensate formed by cracking above
150degree C followed by some Dry Gas.
• Class III:
Source rocks contain mostly Refractory Kerogen. Generation and expulsion
take place only above 150 degree C and petroleum fluid is a relatively dry Gas

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 The Origin of Petroleum

Organic-rich Thermally Matured

Source Rock Organic Matter Oil

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Oil and gas are formed by the thermal cracking of
Kerogen
organic Typesburied in fine-grained rocks.
compounds

• Algae =
Hydrogen rich =
Oil-prone

• Wood =
Hydrogen poor =
Gas-prone

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 Petroleum System: Timing is Critical
Trap Must Be Available Before/During Migration

Accumulation
Processes Generatio Migration and
: n Preservation

Source Migration Reservoir

Elements Rock Avenue and Seal
:
For accumulations to occur, a trap must exist either before or coincident with the time of
migration. The petroleum system events chart helps capture these critical aspects of timing.
 Petroleum System

1) Early Generation Spill Point

Spill Point

Seal Rock
Reservoir Rock (Mudstone)
Migration from (Sandstone)
‘Kitchen’
Gas beginning to
2) Late Generation displace oil

Displaced oil
accumulates
Gas displaces all
oil
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 Several specific forms of hydrocarbons-

• Dry gas- contains largely methane, specifically

contains less than 0.1 gal/1000ft3 of condensable
(at surface T and P) material.

• Wet gas- contains ethane propane, butane. Up to

the molecular weight where the fluids are always
condensed to liquids

• Condensates- Hydrocarbon with a molecular

weight such that they are gas in the subsurface
where temperatures are high, but condense to
liquid when reach cooler, surface temperatures.

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 Several specific forms of hydrocarbons-
• Liquid hydrocarbons-
• commonly known as oil, or crude oil, to distinguish it from
refined hydrocarbon products.

• Plastic hydrocarbons- asphalt

• Solid hydrocarbons- coal and kerogen- (kerogen strictly
defined is disseminated organic matter in sediments that is
insoluble in normal petroleum solvents.

• Gas hydrates-
• Solids composed of water molecules surrounding gas
molecules, usually methane, but also H2S, CO2, and other
less common gases.

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 Hydrocarbon Generation Stages

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• Cross section through part of a sedimentary basin in which a
hydrocarbon source rock layer has been buried to different depths.
• Due to increasing temperatures with increased burial depth, organic
matter within this source rock `cooks', resulting in partial
decomposition and petroleum generation (mature source rock).
• With further burial, organic matter decomposes to generate natural gas
(over-mature source rock).
• Generated petroleum and natural gas are expelled from the source
rock and migrate upward into porous overlying rock layers.
• If appropriate conditions exist, petroleum and natural gas are trapped
and accumulate.
• If appropriate conditions do not exist, natural gas is eventually
released to the atmosphere and petroleum seeps at the surface to form
asphalt (tar) deposits.

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 Expulsion of hydrocarbons from shale source Rocks
• There is compelling evidence that movement of petroleum
from organic-rich shales into sandstones and limestones,
occurs in the subsurface.

• This expulsion of material must occur if crude oil

accumulations are to form, and it is termed primary
migration.

• Earlier studies suggested that this movement occurs with

chemical fractionation: some components are more mobile
than others.

• One of the agents of expulsion at early maturity stages is

compaction, which is not only capable of forcing water, but
also organic components out of the pore network of a
source rock.

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 OIL AND GAS MIGRATION
• Traditionally (Illing, 1933), the process of
petroleum migration is divided into two parts:

• primary migration within the low-permeability

source rocks

• secondary migration in permeable carrier beds

and reservoir rocks.

• It is now recognized that fractured source rocks

can also act as carrier beds and reservoir rocks so
more modern definitions are:

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 OIL AND GAS MIGRATION

• Primary migration of oil and gas is movement

within the fine-grained portion of the mature
source rock.

• Secondary migration is any movement in carrier

rocks or reservoir rocks outside the source rock
or movement through fractures within the source
rock.

• Tertiary migration is movement of a previously

formed oil and gas accumulation.

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 Mechanisms of Migration
• With regard to the mechanisms involved in migration there are seven main
questions to answer.

• When did migration take place?

• What form were the hydrocarbons in when they migrated?

• What moved the hydrocarbons?

• If water was involved: where did the water come from?

• What caused the water to move?

• In which direction did the water move?

• Have much water moved?

Department of Petroleum Technology, University of Karachi

 PRIMARY MIGRATION

• Primary oil migration within a fine-

grained mature source rock with
> 2% total organic carbon (TOC)
occurs initially as a bitumen that
decomposes to oil and gas and
migrates as a hydrocarbon (HC)
phase or phases.
• Type III kerogens are the
• The process of HC generation most likely source.
causes expulsion of petroleum • Migration can also occur in
and is often a more potential aqueous solution for the
mechanism for migration than smallest and most soluble
mechanical compaction.
molecules (methane,
• Generation and expulsion of light ethane, benzene, toluene).
oil, and gas can come from low • Migration by diffusion is not
(< 2%) TOC source rocks without significant.
a bitumen intermediate.

Department of Petroleum Technology, University of Karachi

 PET 631 Migration
• There are two types of migration
when discussing the movement of
petroleum, primary and secondary.

• Primary migration refers to the

movement of hydrocarbons from
source rock into reservoir rock and
it is this type that the following
discussion refers to.

• Secondary migration refers to the

subsequent movement of
hydrocarbons within reservoir
rock; the oil and gas has left the
source rock and has entered the
reservoir rock.
•

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 Primary Migration from shale source Rocks
• A problem in close relation
to the later stage of the
project is the expulsion of
hydrocarbons from source
rock (primary migration).

• The chemical aspects of

this process has been
extensively studied, but the
physical aspects are poorly
understood.

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 Primary Migration

Fig. Generalized view of oil

migration using invasion
percolation concepts
(from Carruthers and Ringrose,
1998).

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 Micro-pressuring.
Mompers [1978] clearly outlines
the characteristics of a source
rock which are important in the
development of micro-pathways
with the rock.
At some point the pressure
increase causes micro-fracturing
in the rock, and the hydrocarbons
migrate into the micro-fractures
which lead out of the source rock.
This concept allows the
hydrocarbons to migrate in a
liquid phase.
This is regarded as the main
mechanism for primary migration
out of the source rock.

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 GENERATION, MIGRATION, AND TRAPPING OF
HYDROCARBONS

Seal

Fault
Oil/water
(impermeable)
contact (OWC)
Seal
Migration route
Seal
Hydrocarbon Reservoir
accumulation rock
in the
reservoir rock
Top of maturity

Source rock

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 Migration through Fractures

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 Mechanics of Secondary Hydrocarbon Migration

• The mechanics of secondary hydrocarbon migration and

entrapment are well-understood physical processes that
can be dealt with quantitatively in hydrocarbon
exploration.

• The main driving force for secondary migration of

hydrocarbons is buoyancy.

• If the densities of the hydrocarbon phase and the water

phase are known, then the magnitude of the buoyant force
can be determined for any hydrocarbon column in the
subsurface.

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 Mechanics of Secondary Hydrocarbon Migration

• Hydrocarbon and water densities vary significantly.

• Subsurface oil densities range from 0.5 to 1.0 g/cc;

subsurface water densities range from 1.0 to 1.2 g/cc.

• When a hydrodynamic condition exists in the subsurface,

the buoyant force of any hydrocarbon column will be
different from that in the hydrostatic case.

• This effect can be quantified if the potentiometric gradient

and dip of the formation are known.

• The main resistant force to secondary hydrocarbon

migration is capillary pressure.

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 Mechanics of Secondary Hydrocarbon Migration

• The factors determining the magnitude of the resistant

force are the radius of the pore throats of the rock,
hydrocarbon-water interfacial tension, and wettability.

• For cylindrical pores, the resistant force can be quantified

by the simple relation: , where Pd is the hydrocarbon-
water displacement pressure or the resistant force, is
interfacial tension, is the wettability term, and R is radius
of the largest connected pore throats.

• Radius of the largest connected pore throats can be

measured indirectly by mercury capillary techniques using
cores or drill cuttings.

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 Mechanics of Secondary Hydrocarbon Migration
• Subsurface hydrocarbon-water interfacial tensions range
from 5 to 35 dynes/cm for oil-water systems and from 70 to
30 dynes/cm for gas-water systems.
• Migrating hydrocarbon slugs are thought to encounter
water-wet rocks.
• The contact angle of hydrocarbon and water against the
solid rock surface as measured through the water phase, ,
is thus assumed to be 0°, and the wettability term, , is
assumed to be 1.
• A thorough understanding of these principles can aid both
qualitatively and quantitatively in the exploration and
development of petroleum reserves.

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 Driving forces for migration:
• Secondary migration is the movement
of hydrocarbons along a "carrier bed"
from the source area to the trap.

• Migration mostly takes place as one or

more separate hydrocarbons phases
(gas or liquid depending on pressure
and temperature conditions).

• There is also minor dissolution in

waterof methane and short chain
hydrocarbons.

• Buoyancy (This force acts vertically

and is proportional to the density
difference between water and the
hydrocarbon so it is stronger for gas
than heavier oil)

• Hydrodynamic flow (water potential

deflect the direction of oil migration,
the effect is usually minor except in
over pressured zones (primary migration))

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 Resisting forces:
Capillary pressure (opposes
movement of fluid from coarse-grain
to fine- grain rock, also the capillary
pressure of the water in the reservoir
resists the movement of oil)

One result of hydrodynamic flow is a

tilted oil-water contact (OWC) in a
trap. OWC is an equipotential
surface, but if the water is flowing the
equipotential surfaces are inclined in
the direction of flow, so the OWC will
be tilted too.

During migration the pressure and

temperature conditions of the
hydrocarbons can change a lot
affecting the phase behavior of the
oil.
•

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 Rate of migration
Rate of migration is controlled by

Darcy's law q= -k/v dp/dz

• (for a single fluid phase)

where q=volumetric flow rate, k=permeability,
v=viscosity, dp/dz=pressure gradient.

Given typical permeabilities of sandstone, and

flow rate of oil can range from 1 to 1000 km
per million years.

This is faster than rate of generation and

expulsion, so oil generation is the rate-
limiting factor.

Because the carrier bed has to reach a

minimum oil saturation before oil can flow,
there is a volumetric loss associated with
migration.

The oil will seek a tortuous path of least

resistance which typically will be a small
portion of the total carrier bed volume

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• Retardatin of buoyant movement as an oil globule (X) is deformed to
fit into a narrow pore throat (Y). The upward buoyant force is partly
or completely opposed by the capillary-entry pressure, the force
required to deform the oil globule enough to enter the pore throat. If
the capillary-entry pressure exceeds the buoyant force, secondary
migration will cease until either the capillary-entry pressure is
reduced or the buoyant force is increased.
 MECHANISM

• Once hydrocarbons are expelled from the source rock in

a separate hydrocarbon phase into a secondary-
migration conduit, subsequent movement of the
hydrocarbons will be driven by buoyancy. Hydrocarbons
are almost all less dense than formation waters, and
therefore are more buoyant. Hydrocarbons are thus
capable of displacing water downward and moving
upward themselves. The magnitude of the buoyant force
is proportional both to the density difference between
water and hydrocarbon phase and to the height of the oil
stringer. Coalescence of globules of hydrocarbons after
expulsion from the source rock therefore increases their
ability to move upward through water-wet rocks
 Two basic types of traps:
Stratigraphic traps are depositional in Structural traps hold oil and gas because
nature. the earth has been bent and deformed in
This means they are formed in place, some way. The trap may be a simple dome
usually by a sandstone ending up (or big bump), just a "crease" in the rocks, or
enclosed in shale. it may be a more complex fault trap like the
The shale keeps the oil and gas from one shown at the right.
escaping the trap.

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 Migration of oil and gas into and out of an anticlinal trap.

Department of Petroleum Technology, University of Karachi