Escolar Documentos
Profissional Documentos
Cultura Documentos
3. Maturity ------------------------------------------------------------(36)
(1)Diagenetic compositional changes in hydrocarbon 7. Modeling ----------------------------------------------------------(80)
(2)Diagenetic change in chemical structure of kerogen (1)Changes in %Ro under different heating rate
Dr. SAMPEI, Yoshikazu (3)Vitrinite Reflectance (2)Computer simulations based on kinetics of isomerization
Professor, Department of Geoscience, Faculty of Science and (3)Data set of kinetic parmeters
(4)Maturity indicator of biomarker
(4)Simulation results
(5)GC/MS SIM chromatogram of oil
Engineering, Shimane University, E-mail:sampei@riko.shimane-u.ac.jp (6)Relationship between two biomarker maturity indicators 1
(7)Relationship between two biomarker maturity indicators 2, 8. Reference ---------------------------------------------------------(84)
(8)Non-biomarker maturity indicators in postmature zone
(9)Respond range of maturity parameter
(10)Origin of methane
Contents
4. Migration and Trap ----------------------------------------------(46)
(1)Primary migration and secondary migration
(2)Porosity and fluid pressurek
1. Fundamentals of Organic Geochemistry ------------------------(4) (3)Porosity and permeability of reservoir rock
(1)Components of oil (4)Microfracturing system in primary migration
(2)Biomarker (5)Diffusion-controlled processes in primary migration
(3)Labeling system (6)Molecular solution in water
(4)Symbols of chemical structure (7)Molecular solution in gas
(5)Modifiers on chemical structure (8)Complex system for oil accumulation
(6)Stereo-isomer (9)Preferential expulsion
(7)Optical isomer
(8)Racemization
(9)Important analytical equipment : GC 5. Source Rock Evaluation -----------------------------------------(55)
(10)Important analytical equipment : GC/MS (1)Standard evaluation sheet for source rock potential
(11)Representative GC/MS result: Selected ion chromatogram (2)Source rock generative potential
(12)Representative GC/MS result: Full scan and mass chromatogram (3)TOC and S2 of shale
(4)Controlling factors of TOC
(5)S2-TOC plot
2. Origin and Formation of Petroleum --------------------------(16) (6)Lacustrine source rock evaluation
(1)Kerogen Type (7)Biomarker as organic source indicator
(2)Depositional environment of kerogen type (8)Biomarker as organic source indicator
(3)Caracterization of Kerogen: bulk composition (9)Age control of the C28/C29 steranes ratio
(4)Kerogen formation: classical and diagenetic path (10)Oxic-anoxic proxy
(5)Kerogen formation: new concept (11)Depositional environment indicator
(6)HI and OI (12)Origin indicator
(7)Van Krevelen diagram and HI-OI (13)Depositional indicator
(8)Rock Eval (14)Origin indicator 2
(9)Interpretation of Rock Eval (15)Origin indicator 3
(10)HI and H/C (16)Porphyrin
(11)Petroleum system (17)Souce rock potential and environmental change
(12)Crude oils characterization
(13)Crude oils characterization 2 6. Oil-Source Rock Correlation and biodegradation ---------(72)
(14)Hydrocarbon compositions (1)Tool for oil-source rock correlation
(15)Terpanes (2)Correlation by n-alkane
(16)Terpanes (3)Correlation by steranes and hopanes
(17)Aromatics (4)Correlation by steranes
(18)Organic sulfur compounds (5)Confidence of oil-source rock correlation
1. Fundamentals of Organic Geochemistry 1-(1) Components of oil
Asphaltens:
Higher molecular weight (500-1500)
NOS/polar compound; soluble in
CS2; insoluble in n-C6H8 or n-C5H10
Resins:
Higher molecular weight (less than
500) NOS/polar compound; soluble in
n-C6H8 or n-C5H10
Molecular sieve:
Separation based on molecular size by
e.g. zeolite; small molecules become
trapped in the crystal lattice.
Urea adduction:
Small molecules become adducted by
urea crystal (NH2CONH2); use to
concentrate e.g. steranes.
Tissot and Welte (1984)
1-(2) Biomarker
Useful tool to know:
Origin of organic matter; Depositional environment;
Maturity; Correlation between oils and source rock.
Steranes
Hopanes
Three-dimensional
structure
To know:
Maturity
(Origin)
= Stereochemistry
bis=di
tris=tri
tetrakis=tetra
pentakis=penta
hexakis=hexa
Nor-: one less carbon on structure. Des-A: loss of A from structure. Iso-: methyl
shifted on structure. Neo-: methyl shifted from C18 to C17 on hopane.
Important concept to
understand maturity indicators
of biomarker
Chiral molecule:
The name is given to a
substituent with an asymmetric
carbon at which optical
isomers may occur.
Peters and Moldowan (1993)
1-(7) Optical isomer
Epimer
Enantiomer
Enentiomorph
Antimer
The biological epimer
20R-C29-5α, 14α, 17α(H)-sterane
changes to the geological epimer
20S-C29 5α, 14α, 17α(H)-sterane
GC:
The separation of mixtures of
compounds by partition between
a mobile gas phase and
stationary liquid phase is called
gas chromatography
(Miles,1994).
Steranes and hopanes have specific fragment ions m/z=217 and m/z=191,
respectively.
m/z=217
m/z=217 5 9 C sterane 20R
28
C27 sterane 20R (ergostane)
(cholestane)
13
C29 sterane 20R
(stigmastane)
6
12
7 11 15
10 14
8 16
Diacholestane 20R 4 3
2
17 18
1
C30Hopane
m/z=191
C31Homohopane (S,R)
Tm C32(S,R)
C34 (S,R)
C33 (S,R) C (S,R)
35
Ts
Cholesterol
HO
Stigmasterol
HO
24α-ethylcholesta-5,22E-dien-3β-ol
As macerals (morphology) 2. Origin and Formation of Petroleum
2-(1) Kerogen Type
Kerogen: Insoluble; preserved in sedimentary rocks
Type-I
Type I (very oil prone): amorphous
hydrogen-rich; algal in anaerobic; especially lacustrine.
Type I
Type III Type III
Type II
Type II
500-2500m without supply of clay
Immature type I :
high H/C about 1.7 and low O/C about
0.05.
Immature type II :
medium H/C about 1.3 and medium
O/C about 0.1
lignin
HI = S2/TOC
Example:
S2=4(mgHC/gRock)
TOC=2(%)
HI = 4/(2/100) = 200 (mgHC/gC)
Anhydrous pyrolysis
Institute Francais du
Petrole (IFP)
HI: S2/TOC
OI: S3/TOC
Tmax: ºC
<435 ºC (immature)
435 to 460 ºC (mature)
Tissot and Welte (1984) >460 ºC (post mature)
Whelan and Thompson-rizer
(1993)
C14H10 : H/C=0.71
2-(11) Petroleum system
Anoxic condition:
kerogen survives oxidation
Aromatics:
absent in recent
sediments;
produced in the
early diagenesis;
decomposed in the
catagenetic
Tissot and Welte (1984)
2-(14)
Hydrocarbon compositions
alkanes (n-alkane)
iso-alkane
Cycloalkanes
mono-aromatics
di-aromatics
organic sulfur compounds poly-aromatics
organic nitrogen compounds
organic oxygen compounds.
Sesterterpanes (C25):
Acyclic
Tricyclic
tetracyclic
head
Triterpanes (C30):
Acyclic
Tricyclic
pH control
Neutral nitrogen
Basic nitrogen
Mainly due to
biodegradation
1
2
homohopanes
average equilibrium ratios
C31, C32, C33, C34, and C35 are 0.55, 0.58, 0.60, 0.62
Peters et al. (2005) and 0.59 (Zumberge, 1987)
3-(5) GC/MS SIM of oils
Biomarker: broken by thermal
cracking and aromatization
17α-hopane decreases with
increasing maturity
The less stable Tm decreases relative
Peters et al. (2005) to Ts with increasing maturity.
The C19-C29 tiricyclic terpanes can
be used as fingerprint.
C27 hopanes
Ts/Tm; Ts is C27 18α-trisnorhopane
(18α-22,29,30-trisnorhopane) and
Tm is C27 17α-trisnorhopane (17α-
22,29,30-trisnorhopane) and less
stable than Ts.
αα means:
C29- 14α, 17α(H)-sterane
ßß means:
C29- 14ß, 17ß (H)-sterane
Peters et al. (2005)
ßß(ßß+αα)-C29-steranes:
From near-zero to about 0.7
20R or 20S
(equilibrium at 0.67-0.71;
17α or 17ß seifert and Moldowan, 1986).
14α or 14ß
3-(7)
Different isomerization rate
(diagenesis to catagenesis)
In low maturity:
Hopane isomerization
increases faster than sterane.
In high maturity:
Hopane isomerization
increases more showly than
sterane.
3-(8)
Aromatic compounds are useful
as a maturity indicator in
postmature zone.
MPI-3
Sampei et al. (1994)
Ro=0.79*MPI-3-0.30
(Ro=0.4-1.6).
Peters et al. (2005)
3-(9)
Range of maturity parameter
20S/(20S+20R) steranes,
22S/(22S+22R) hopanes:
up to 0.8 and 0.55 in %Ro
Dia/(Dia+Reg) steranes,
Ts/(Ts+Tm):
up to 1.4 in %Ro
(Dia/(Dia+Reg) steranes have a
disadvantage that is influenced
by depositional environment and
clay catalyst and Ts/(Ts+Tm)
depends on source.)
MA: mono-aromatic steroid
TA: triaromatic steroid
Etio: Etio-porphyrin is thermally
derived from DPEP,
DPEP:deoxo-phylloerythro-ethi-
prophyrin.
3-(10) Origin of methane Cross plots of δ13C to methane/total
biogenic or thermogenic hydrocarbon (C1/ΣCn)
Biogenic methane
δ13C about -60 to -80 ‰ vs PDB
very high C1/ΣCn more than 0.97
Thermogenic methane
δ13C more than -50 ‰ vs PDB
low C1/ΣCn down to 0.6.
Secondary migration:
From the source rock through
permeable rocks along faults
and conduits to trap
Great migration distance in the
order of 100km unless special
big unconformity
Interrelationship of:
Porosity of source rocks,
Fluid pressure,
Temperature,
Depth
Primary migration
efficiencies of between 5
and 80 % of available oil
are believed.
10 % (porosity) and
1 m-darcy (permeability).
Hydrocarbons move
independently from places
of higher concentration to
places of lower
concentration.
Large faults
make complex
for oil trap
system.
TOC,
Rock-Eval S1,S2
HI
OI
%Ro
Tmax
Biomarker compositions
For considering:
Kerogen type
Depositional
environment,
Hhydrocarbon potential
Maturity
Peters et al. (2005)
5-(2) Source rock generative potential
To assess the source rock generative potential, the most basic parameters are
TOC and S2.
More than 1% of TOC and 5mgHC/g-rock is a good source rock, and less than
0.5% of TOC and 2.5mgHC/g-rock is a poor source rock.
5-(3) TOC and S2 of shales
Primary productivity
Oxic-anoxic
condition
Sedimentation rate
Sedimentation rate is
often a key.
Ibach (1982)
Up to about 0.1mm/y
TOC increases with
increasing SD.
Steranes and hopane distributions are good indicators for organic source.
5-(8)
Biomarker as organic source
indicator 1
High Pr/Ph ratios >3.0 indicate terrestrial organic matter input under oxic
conditions and low values <0.6 typify anoxic (Peters and Moldowa, 1993).
Oleanane/(Oleanane+C30hopan
e) ratio:
Highly specific for higher plant
input
During transgressive, TOC and HI are high, and terrigenous input and
degradation are low.
n-Alkane distribution
is useful for
correlation.
Between bitumens
from source rock and
oils
Curiale (1993)
6-(3)
Correlation by steranes and
hopanes
Curiale (1993)
6-(4)
Correlation by steranes
Diasterane composition
reflects rock faces such as
clay stone.
Hydrocarbon gases
→ n-alkanes
→ iso-alkanes
→ isoprenoids
→ aromatics
→ poly-aromatics
→ steranes&hopanes
Rullkotter (1993)
Geothermal gradient (℃/km)
Depending upon
1. thermal conductivity of rock strata,
2. heat flow
3. water movement
World average:25℃/km
5℃/km: ex. Andros Island in the Bahamas
90℃/km: ex. Walio oilfield in the Sarawati Basin, indonesia
Heatflow(Q) Q=k×ΔT
k:thermal conductivity
ΔT:geothermal gradient
1 (HFU: heatflow unit) = 0.42×10-5 (Wm-2)
World average: 0.63×10-5 (Wm-2)
7-(2) Kinetics of isomerization
Activation energy (E); Pre-exponential factor (A)
C: concentration of kerogen, C0: initial concentration of kerogen, k: rate constant,
t: time, A: pre-expornential factor, E: activation energy, R: gas constant 1.987
cal/deg, T: absolute temperature, q: heatig rate, (5) by Alexander et al. (1986)
C = C 0 e − kt (concentration chan ge) - - - - - - - -Sampei
- - - - - -and
- - - Suzuki
- - - - - -(2005)
------------- (1)
dT ∆T
=q ( = q)
dt ∆t ----------------------------------------------------------- (3)
A T − E / RT
q ∫T 0
k = e dT
---------------------------------------------------------- (4)
ART 2 − E / RT RT RT 2 ---------------------------------------- (5)
k=( )e 1 − 2 ( E ) + 6 ( E )
qE
Cretaceous
Age m.y
by PRA software
La Cira 1625K well, Colombia
Cretaceous
Age m.y
by PRA software