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Geochemistry in petroleum exploration 1

Geochemistry in petroleum exploration 1

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GEOCHEMISTRY

GEOCHEMISTRY IN PETROLEUM EXPLORATION

1 INTRODUCTION ............................................................................................................................. 2
1.1 PHILOSOPHY......................................................................................................................................... 2
1.2 FORMATION OF OIL & GAS................................................................................................................... 2
1.2.1 Diagenesis .................................................................................................................................... 2
1.2.2 Catagenesis................................................................................................................................... 2
1.2.3 Metagenesis .................................................................................................................................. 2
1.2.4 Migration...................................................................................................................................... 3
1.3 APPLICATION ....................................................................................................................................... 3
2 ORGANIC FACIES .......................................................................................................................... 3
2.1 THE CARBON CYCLE............................................................................................................................. 3
2.2 FACTORS INFLUENCING ORGANIC RICHNESS ....................................................................................... 3
2.2.1 Productivity .................................................................................................................................. 3
2.2.2 Preservation.................................................................................................................................. 3
2.2.3 Dilution......................................................................................................................................... 4
3 ORGANIC CHEMISTRY AND ISOTOPES.................................................................................. 4
3.1 NAMES & STRUCTURES........................................................................................................................ 4
3.1.1 Hydrocarbons ............................................................................................................................... 4
3.1.2 Heterocompounds (NSO).............................................................................................................. 5
3.2 STEREOCHEMISTRY & STRUCTURES.................................................................................................... 5
3.3 REACTIONS........................................................................................................................................... 5
3.4 ISOTOPES .............................................................................................................................................. 5
4 KEROGEN......................................................................................................................................... 5
4.1 INTRODUCTION..................................................................................................................................... 5
4.2 FORMATION.......................................................................................................................................... 5
4.3 COMPOSITION....................................................................................................................................... 6
4.4 MATURATION ....................................................................................................................................... 6
5 RESERVOIR TRANSFORMATIONS............................................................................................ 7
5.1 WATER WASHING AND BIODEGRADATION............................................................................................ 7
5.1.1 Water washing .............................................................................................................................. 7
5.1.2 Biodegradation ............................................................................................................................. 7
5.2 OIL SEGREGATION BY GRAVITY........................................................................................................... 7
5.3 LEAKAGE OF CAP ROCK, DYSMIGRATION THROUGH FAULT ................................................................ 7
5.4 INFILLING RESERVOIR WITH GASES, NATURAL DEASPHALTING .......................................................... 7
5.5 THERMAL CRACKING, MATURATION ................................................................................................... 7

JCD 09/2003 1/7
GEOCHEMISTRY

1 INTRODUCTION
1.1 PHILOSOPHY
We must understand how oil & gas are formed and use this knowledge to locate new HC reservoirs
1.2 FORMATION OF OIL & GAS
50°C
150°C
120°C
















250°C






o Example of natural gas characteristics according to their maturity:

Evolution C1/C2+ IC4/nC4
Early diagenesis >0.97 >6
Catagenesis <0.98 <1
Metagenesis >0.97

o Plants and algae’s are buried in fine grained sediments and absence of O
2
.
o The organic matter is transformed in kerogen by low temperature chemical & biological
reactions.
o The large molecules of kerogen are the precursors of oil & gas.
1.2.1 DIAGENESIS
o Methanogen microorganisms transform debris in biogenic CH
4

1.2.2 CATAGENESIS
o Temperature rises and the bacterial action stops (temp >80°C)
o Thermal reactions break the kerogen in smaller molecules called bitumen in an early
stage, then, with increasing maturity, to oil, condensate and finally gas.
1.2.3 METAGENESIS
o The thermal process continues and creates smaller molecules: thermal CH
4

JCD 09/2003 2/7
GEOCHEMISTRY
1.2.4 MIGRATION
o The HC are expelled from the source rock and migrate to a trap where it will
accumulate.
1.3 APPLICATION
3 types of geochemical models : organic facies, thermal maturity and volumetric.
2 ORGANIC FACIES
2.1 THE CARBON CYCLE

Oxydation






















o Most of organic matter is returned to the atmosphere through the carbon cycle (photosynthesis),
only 1% of the photosynthetic production is preserved in sediments.
o The oxidation in the sediments (down to 300m) will bring the Total Organic Carbon (TOC)
value down to 0.1%.
2.2 FACTORS INFLUENCING ORGANIC RICHNESS
The 3 factors influencing the amount of organic matter in a sediment are: productivity, preservation
and dilution.
2.2.1 PRODUCTIVITY
o Shallow water is the most productive environment (Plants + light: 20 000t/km
2
)
o In high water zones, water upwelling can increase productivity
2.2.2 PRESERVATION
o Preservation is the most important factor for organic richness. It is linked to:
Anoxia : linked to stagnancy, the sediments are very dark.
Oxygen Minimum Layer (OML): the O
2
request is higher than the production, due to decay of
organic matter falling from the upper photic zone.

JCD 09/2003 3/7
GEOCHEMISTRY


High O
2
request, no
vertical water
movement
Less O
2

demand,
Photic zone




















Rapid burial

2.2.3 DILUTION
If the burial becomes extremely rapid, the dilution may become higher than the preservation (Specially in
shales)
3 ORGANIC CHEMISTRY AND ISOTOPES
3.1 NAMES & STRUCTURES
3.1.1 HYDROCARBONS
o Only C & H
Alkanes or paraffins or saturated:
• straight line = n-alkanes (C
n
H
2n+2
) (normal…)
• Non linear = iso, meta, etc or use the methyl (CH
3
) radical

2 different heptanes











• Cyclic (C
n
H
2n
) every C is linked to 2 C and 2 H
• Isopropenoids: straight chain of C with a methyl on every 4 C

Unsaturated:
JCD 09/2003 4/7
GEOCHEMISTRY
• Able to combine with additional H
• Alkenes or olefins: double bond between C’s : react easily and do not persist in geological
environment
• Aromatics are cyclic alkenes but they are stable (BTX): they alternate single and double
bonds (delocalised electron) between the C’s
3.1.2 HETEROCOMPOUNDS (NSO)
o Contains also N, O or S
o Very often converted to HC during dia & catagenesis
o Porphyrins (from chlorophyll) are often present in oil
o Asphaltenes: big , highly aromatic molecules
3.2 STEREOCHEMISTRY & STRUCTURES
o Stereochemistry: 3D representation of the molecules
o Isomer: Same chemical formula but different atomic arrangement.(ie; nC4, iC4)
3.3 REACTIONS
o Oxidation: loss of e
-
which goes to the oxidation agent, or loss of H
o Reduction: gain of e
-
which comes from the reduction agent or gain of H
o Isomerisation: an isomer is converted to another
3.4 ISOTOPES
o Variation of the number of neutrons
4 KEROGEN
4.1 INTRODUCTION
o Kerogen = large organic matter molecules, insoluble in organic solvents.
o Bitumen = soluble portion.
4.2 FORMATION






















JCD 09/2003 5/7
GEOCHEMISTRY

4.3 COMPOSITION


















No HC
Produces mainly gas
Produces liquid HC
Rare, produces liquid HC

Maceral equivalent of a mineral for organic matter

4.4 MATURATION
o Maturation is due to high temperatures during a long time























Van Krevelen diagram
o A mature kerogen becomes more aromatic , as these molecules can stack neatly, the
reflectance increases. The vitrinite reflectance assesses the kerogen maturity.
JCD 09/2003 6/7
GEOCHEMISTRY

5 RESERVOIR TRANSFORMATIONS

Two types of transformations:
o Non thermal process
Water washing
Biodegradation
Leakage, transmigration
o Thermal process :
Cracking
Deasphalting

5.1 WATER WASHING AND BIODEGRADATION
o Unable to differentiate the 2 phenomenon as they occur frequently together and
biodegradation hides the water washing effect.
5.1.1 WATER WASHING
o affects high soluble components: benzene, toluene, light alkanes.
5.1.2 BIODEGRADATION
o affects n alkanes.
o GOR, light HC content increase and API gravity decrease.
o Viscosity, sulfur content increase.
o Temperature above 80°C will kill bacteria and stop biodegradation. (around 2000m deep)

5.2 OIL SEGREGATION BY GRAVITY
o Can be reversed ! (top with a lot of gas but less pressure than the bottom or different pore
sizes)

5.3 LEAKAGE OF CAP ROCK, DYSMIGRATION THROUGH FAULT
May result in 2 reservoirs, the upper one with high API gravity (light oil or gas), the lower one with
residual heavy HC and low API gravity.

5.4 INFILLING RESERVOIR WITH GASES, NATURAL DEASPHALTING
o Deasphalting may be due to gas injection (i.e. heptanes) or thermal cracking, the result is
lighter oil and solid residues.
o When the oil becomes lighter, the asphaltenes become less soluble and precipitate.
o Deasphalting brings an API gravity increase and a sulfur content decrease.

5.5 THERMAL CRACKING, MATURATION
o Function of time and temperature (linked to depth).
o Variation of depth, due to tectonic movements can stop or restart cracking process.
o With maturity, API gravity increases , Pour point and viscosity decrease.
o Break the molecules in lighter ones, the high maturity produces dry gas.
o The iC4/nC4 ratio will be high (i.e. > 8) in an immature HC (diagenesis) and will decrease
(ie <1) in the maturity zone (Catagenesis), as maturation creates predominantly n alkanes.
JCD 09/2003 7/7

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