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Biography
New Applications in
Petroleum Geochemistry (Part I)
Calgary
the Netherlands
Stanford
New Orleans
Muscat
Peter Nederlof
Petroleum Geochemist with Shell International E&P
p.nederlof@shell.com
Contents
Part I
Background
- Carbon, Carbon Cycle, Source Rock Deposition
and Source Rock Evaluation
Carbon
Methane
CH4
Ethane
CH3CH3
H
H
CH 2
CH 2
CH 2
CH 2
Hexane
C6H12
H
H
n-Butane
Propane
CH3CH2CH3
iso-Butane
CH(CH3)3
CH3CH2CH2CH3
H
H
CH 3
Benzene
C6H6
C
H
C
C
C
CH 3
C
H
CH 2
CH 2
CH 2
CH 2
(CH)
2n
Large molecules
occurs in all organic life and is the basis for organic chemistry
Elemental Composition
C
Carbohydrates
44
50
Lignin
63
0.1
0.3
31.6
Proteins
53
17
22
Lipids
76
12
12
Petroleum
80
13
0.5
0.5
6 protons
+ 7 neutrons
Carbon
Isotopes
Isotopes are atoms with the same number of protons, but different number of neutrons
Two naturally occurring, stable isotopes: 12C (98.9%) and 13C (1.1%)
One naturally occurring, unstable isotope: 14C, (half life of 5730 y)
12C-12C
and 12C-13C have different bond strength and (bio)chemical reactions therefore
show carbon isotope fractionation
Organic matter is depleted in 13C compared to carbon in carbonate rocks or CO2 in the
atmosphere
13C
(delta C 13)
13Csample =
x 1000
-34
-32
-30
Isotopically Heavy
-28
-26
-24
-22
-20
Tertiary
Kalash Fm.
Sirt Fm.
Rachmat Fm
Etel Fm.
Cretaceous/Nubian
Triassic
Silurian Shales
www.physicalgeography.net
CO2
Atmosphere
C
Plant Life
Degradation
Respiration
99.9 %
0.1 %
Sediment
Sink
PC
PP TR
4500
Glaciations
4000
3500
3000
2500
2000
1500
1000
500
0
600
PC
500
400
300
C PP TR
Time (Ma)
200
100
CO2
Atmosphere
0.02 %
Degradation
Respiration
C
Plant life
Sediment
Sink
99.98 %
10
Carbon Reservoirs in Gt
Reduced Carbon
Oxidized Carbon
600
Atmosphere
Oceans
Surface water Biota
DOC
Carbonate Carbon
3
700
Land biota
Soil and Detritus
Sediments
610
1,560
12,000,000
39,000
Geosphere
48,000,000
CO2 levels during early Phanerozoic were 25 times current level (350 ppm)
11
Conclusion
- Most of the organic matter sits in the subsurface (and is depleted in 13C)
Source Rock
Evaluation
(Petroleum Geochemistry)
12
13
14
Phytoplankton
Zooplankton
Algae, bacteria etc.
Land plants
> 99%
< 1%
Photosynthesis
Carbon Cycle
0.02 %
Degradation
Respiration
C
Plant life
Sediment
Sink
15
Primary Productivity
Sunlight
Carbon Dioxide - Oxygen
Nutrients; N, P, Si, Fe, Ni, V, Zn, Cu
January
July
Zooplankton
Phytoplankton
Nutrients
Sunlight
December
16
Ceratium hirundinella,
(Dinoflagellate)
River input
Black Sea
The influx of fresh waters results in severe density stratification, which inhibits the
mixing of the bottom waters with the surface waters. The dissolved oxygen is
removed from the water by the oxidation of organic matter.
This leads to strong anoxia with dissolved H2S at depth.
17
Lakes
stratification
Flux of terrigenous
and marine OM
Low oxygen
Pro-deltaic shales
Restricted bottom
water circulation
Carbonate build-ups
Intra-basinal sags
18
Preservation: Upwelling
Offshore winds
Area of high productivity
OMZ
N P Si
5000
PC
PP TR
4500
Glaciations
4000
3500
3000
2500
2000
1500
1000
500
0
600
PC
500
400
300
C PP TR
Time (Ma)
200
100
19
shelf anoxia
high productivity
strongly stratified water column
OMZ
Polar Region
ice
dense oxygen rich btm water
Primary productivity
Water depth
Water Column Stratification
Redox state of the water column
Sedimentation rate
Photosynthesis
CO2
Atmosphere
Carbon Cycle
0.02 %
Degradation
Respiration
C
Plant life
Sediment
Sink
20
14,000
TOC wt%
15,000
S2 mgHC/g rock
16,000
17,000
18,000
19,000
20,000
21,000
22,000
23,000
24,000
0
10
11
12
13
14
15
..
Richness
..
..
Solvent Extraction
..
Type, Maturity
Thickness
SPI calculation
..
..
Compositional kinetics
..
.. and then there are complications like oil-based mud, mud additives,
cuttings vs. core samples, picked samples vs. raw ditch, burnt-out source rocks,
carbonate vs. shale source rocks, differences between geochem labs ..
21
None
Poor
Fair
Good
Excellent
0.0 0.5
0.5 1.0
1.0 2.0
2.0 5.0
>5.0
0.0 0.2
0.2 0.5
0.5 1.0
1.0 2.0
>2.0
temperature
Generation Potential
Tmax
Trapping
of CO2
time
S1
Thermal
extraction
S2
Pyrolysis
S3
CO2 release
22
1800
2000
2000
2200
2200
2400
2400
2600
2600
Depth (m)
Depth (m)
1800
2800
2800
3000
3000
3200
3200
3400
3400
Rock Eval S2
TOC
3600
3600
3800
3800
0
10
15
TOC (% wt)
20
25
Tmax (C)
23
2200
2600
40
R ock Eval S2
Depth (m)
2400
TOC
2800
3000
0
10
15
TOC (%wt)
20
25
30
HI = 770
20
10
0
0
TOC
MW
(Dalton)
H/C
O/C
Aliphatic C
(%)
Main
functional
group
Type I
21,000
1.64
0.06
74
Ether
Type II
26,000
1.34
0.20
51
Ester
Type III
26,000
1.06
0.28
38
Phenol
After Vandenbroucke
(2003)
24
Type II
Type III
HI of 300
25
Silurian, Syria
Good, post mature, Type II source rock (TOC-1.6%).
Photomicrograph, showing lenses of SOM associated with framboidal pyrite.
26
27
Conclusions (Part I)
- Most of the organic matter sits in the subsurface (and is depleted in 13C)
- Organic matter in the subsurface is concentrated in a wide variety source rocks
Next question:
How are oil and gas generated from source rocks?
28
New Applications in
Petroleum Geochemistry (Part II)
Contents
Part I
Background
- Carbon, Carbon Cycle, Source Rock Deposition
and Source Rock Evaluation
29
Kerogen:
Kinetics:
Kerogen
k1
k2
k3
kn
Petroleum
rate
=k x
rate i i==-dx
-dxi/dt
i/dt = ki i xi i
-Eii//RT
RT
kkii== A
Aiiee -E
Arrhenius
(Nobel laureate 1903)
30
1. Discrete Distribution of Ea
0.3
Ea (kcal/mol)
0.2
67
63
55
51
59
0.1
Ea mean
3. Single start and end Ea
Ea start
Ea end
58
Coaly Kerogen
(Type II/III)
59
65
1.0
SR Conversion
Lacustrine Kerogen
(Type I)
0.8
0.6
0.4
0.2
o
*5 C/Ma
Ea (kcal/mol)
Ea (kcal/mol)
31
Compositional Kinetics
Results from Laboratory and Mathematical Simulation
Mathematical
Simulation
Mathematical
Simulation
Predicted
Product Mix from Shells GENEX5 modelling software
(Shell)
(Shell)
Laboratory
LaboratorySimulation
Simulation
(California
(CaliforniaInstitute
Instituteof
ofTechnology)
Technology)
C3-5
C6-14 Sat
C2
C15+ Sat
C6-14 Aro
C15+ Aro
32
90 C
150 C
Basin Modeling
33
Next question:
Where does the generated oil go?
34
Oil Analysis:
Gas Chromatography
Algal SR
Thailand
Carbonate SR
Oman
Landplant SR
Far East
35
9,262ftft
8,120
9,262ft ft
8,120
9,262 ft
10,000 ft
6,836 ft
36
Molecular Fossils
Cholesterol
Cholestane
ant
bund
a
t
s
o
he m
earth
are t icals on
s
d
i
em
ano
Hop tural ch
na
37
Question:
Is there more than one oil source
rock in the Abu Gharadig Basin,
Egypt ?
38
Safa
Khoman B
Bahariy
a
Kharita
Alamein
Alam El Bueib
Masajid
Khatatba
Source Rock
39
n-Alkane CSIA low mature Abu Roash and highly mature Khatatba oils
C17
C27
-21.0
-22.0
-23.0
-24.0
BED 4-1
Kharita 3636m
BED 4-1
Kharita 3696m
-27.0
-28.0
C17
-29.0
-30.0
C27
-31.0
C9
C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28
C28
C29
BED 4-1
Abu Roash-F Oil
2946 m
C27 Sterane
C28 Sterane
C29 Sterane
C27
C29
C28
BED 4-1
Kharita Oil
3636 m
40
C29
24/4
Tm
Ts
C30
BED 4-1
Kharita oil
3636 m
C29
Tm
24/4
Diahopane
Ts
Answer:
There are 2, may-be even 3 source
rocks in the Jurassic Khatatba Fm.
41
- Oil and gas are formed through the thermal cracking of kerogen, a process
that can be simulated in the lab and modeled accurately
- Petroleum Geochemistry can help identify new opportunities for oil and gas
Exploration by mapping the hydrocarbon habitat of a sedimentary basin
42
New Applications in
Petroleum Geochemistry (Part III)
Contents
Part I
Background
- Carbon, Carbon Cycle, Source Rock Deposition
and Source Rock Evaluation
43
2.
3.
1. Operational
Geochemistry
Mud Gas Logging
44
Logging
While
Drilling
45
Intake Probe
46
Component
FLEX FLAIR
MDT
78.5
76.1
Ethane
9.0
10.0
Propane
5.5
6.6
i-Butane
1.2
1.2
2.9
Methane
n-Butane
2.5
i-Pentane
1.3
1.1
n-Pentane
1.3
1650
1.2
1605
31
29.7
0.55
0.47
GOR
API
Viscosity
47
23050
23100
23150
23200
23250
23300
23350
23400
23450
23500
0
3000
6000
9000
12000
15000
48
-65.0
-55.0
-45.0
-35.0
10,000
TT
12,000
14,000
KK
16,000
18,000
20,000
JU
22,000
24,000
26,000
Biogenic
Thermal
-65.0
-55.0
-45.0
-35.0
7,000
8,000
9,000
10,000
11,000
12,000
13,000
14,000
15,000
16,000
17,000
18,000
19,000
LK?
20,000
21,000
22,000
23,000
M16.5
24,000
Salt
25,000
26,000
27,000
Biogenic
Thermal
49
-65.0
-55.0
-45.0
-35.0
7,000
8,000
9,000
10,000
11,000
12,000
13,000
14,000
15,000
16,000
17,000
18,000
19,000
20,000
21,000
22,000
23,000
24,000
25,000
Biogenic
Thermal
A
B
C
50
51
52
D2-NC41
B3-NC41 B1-NC41
E1-NC41
D1-137
C1-137
C1-NC41
A1-NC146
B1-NC87
K1-NC35A
A1A-NC87
A2-137
C1-NC35A
H1-NC41
K1-NC41
L1-137
E1-NC35A
F1-NC41
L1-NC41
J1-NC35A
J1-NC41
B1-NC120
A1-NC12
A1-NC120
A1-NC173
A1-NC42
E1-87
A1-87
A1-89
C1-NC129
H1-87
A1-88
D1-88
E5-16
S13-6
FF27-6
53
Eocene
Marine shales (Boudabous)
Upper Cretaceous
Sirte/Rachmat Shales/Etel? Marine
shales
Silurian
Tannezuft Equivalent Marine Shales
D2-NC41
B3-NC41 B1-NC41
E1-NC41
D1-137
C1-137
A2-137
C1-NC41
C1-NC35A
H1-NC41
K1-NC41
L1-137
A1-NC146
B1-NC87
K1-NC35A
A1A-NC87
E1-NC35A
F1-NC41
L1-NC41
J1-NC35A
exploration
explorationwildcat,
wildcat,drilled
drilledinin1985
1985
targeted
basal
carbonates
targeted basal carbonatesofofthe
theLower
LowerEocene
Eocene
all
allreservoir
reservoirsections
sectionswater
waterbearing
bearing
no
nosignificant
significanthydrocarbon
hydrocarbonshows
shows
plugged
and
abandoned
plugged and abandoned
J1-NC41
B1-NC120
A1-NC12
A1-NC120
A1-NC173
A1-NC42
E1-87
A1-87
A1-89
C1-NC129
H1-87
A1-88
D1-88
E5-16
S13-6
FF27-6
54
4600
Whole Extract GC
9270 - 9580 ft
5600
6600
9940 10,140 ft
7600
8600
10,400 10,750 ft
9600
110600
0600
12,000 - TD
111600
1600
55
Whole Extract GC
22
n-alkane CSIA
-24.0
30
-25.0
-26.0
-27.0
-28.0
17
-29.0
-30.0
-31.0
-32.0
Steranes
29
C
33
C
31
C
32
C
30
C
29
C
28
C
27
C
26
C
25
C
24
C
23
C
22
C
21
C
20
C
19
C
18
C
17
C
16
C
15
C
14
C
13
C
12
C
11
-33.0
Terpanes
27
Ts
28
32
35
24T
1 gram
C1
C2
C3
iC4
nC4
iC5
nC5
-15.0
-20.0
-25.0
-30.0
-35.0
-40.0
-45.0
-50.0
-55.0
-60.0
56
C2
C3
iC4
nC4
iC5
nC5
-20
-25
-30
-35
-40
-45
-50
-55
57
3. Unconventional
Resources
Shale Gas
58
120
> 500 MMBoe
100
80
60
40
20
19
18
19 . 1
21 92
19 . 1 1
24 92
19 . 1 4
27 92
19 . 1 7
30 93
19 . 1 0
33 93
19 . 1 3
36 93
19 . 1 6
39 93
19 . 1 9
42 94
19 . 1 2
45 94
19 . 1 5
48 94
19 . 1 8
51 95
19 . 1 1
54 95
19 . 1 4
57 95
19 . 1 7
60 96
19 . 1 0
63 96
19 . 1 3
66 96
19 . 1 6
69 96
19 . 1 9
72 97
19 . 1 2
75 97
19 . 1 5
78 97
19 . 1 8
81 98
19 . 1 1
84 98
19 . 1 4
87 98
19 . 1 7
90 99
19 . 1 0
93 99
19 . 1 3
96 99
19 . 1 6
99 99
20 . 2 9
02 00
.2 2
00
5
59
Seepage to
surface
Migration
losses
Sub-economic
traps
Amount
generated
Amount trapped
60
Barnett Shale
Self-Sourced Reservoir
Organic-Rich Shale (TOC = 4-6 wt%)
Complex Lithology
Low Porosity (ave. 3-8%)
Low Perm (Generally <0.01d)
61
Barnett
Mississippian Type II SR
wet
62
eerraattiioonn
n
e
n
G
e
.
11. G
ntiioonn
22.. RReetteent ibiilliittyy
uc ib
33.. PPrroodduc
Conversion
1.0
0.8
0.6
0.4
0.2
0
0.4
0.6
1.2
2.0
Maturity (VRE)
63
Conventional PVT
properties are irrelevant?
Resv
P&T
4000
Calc
Data
Calc (cut Pdp - C16+)
3500
3000
P (psia)
2500
2000
Gas + Liquid
(Saturated Wet Gas)
1500
1000
500
0
-100
100
200
300
400
500
600
T (F)
64
eerraattiioonn
n
e
G
n
e
.
11. G
ntioonn
22.. RReetteentiibiilliittyy
uc ib
33.. PPrroodduc
adsorbent
All gases tend to adsorb to solid surfaces
below their critical P/T point
a) Physical adsorption (van der Waals)
b) Chemical adsorption (chemisorption)
Langmuir Isotherms
Barnett Shale
100
80
60
40
T =145 F
T =175 F
20
0
0
1000
2000
3000
4000
Pressure (psi)
65
= sat
bP
1 + bP
V = Vsat
bP
1 + bP
H
b = b0 exp
RT
q = fractional coverage
qsat = saturated fractional coverage
b = Langmuir parameter
R = 10.73 psi ft3/lbmol/R
H = heat of adsorption (kJ/mol)
80
60
40
20
0
0
1000
2000
3000
4000
66
n
eerraattiioon
n
e
n
G
e
11.. G nttiioonn
te n
22.. RReete ucciibbiilliittyy
od u
33.. PPrrod
Inside a sweet-spot,
well productivity
depends on completion
Though the core area is commonly referred to as Denton, Wise and Tarrant counties, the true sweet spot has
been the Newark East Field, which has been extensively drilled.
Results outside Newark East have not been as impressive. However, another sweet
spot appears to be developing in Johnson County, which looks superior to much of the core acreage beyond
Newark East.
67
68
Acknowledgments
Andy Bell (Shell)
Johan Buiskool Toxopeus (Shell)
Andrew Murray (Woodside)
Shannon de Groot (EAGE)
Questions, Comments?
p.nederlof@shell.com
69
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56
70