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SLT Middle East 2008

New Applications in Petroleum Geochemistry
Dr. Peter Nederlof

Biography

Peter Nederlof is Shells principal technical expert for geochemistry

and responsible for a global skill-pool of some 60 petroleum
geochemists. Peter has a Ph.D. in Chemistry from the University of
Amsterdam and did a postdoctoral fellowship in Natural Product
Chemistry at Stanford University in California. Peter joined Shells
Fine Chemicals Research Group in Amsterdam in 1979 and moved
upstream to the Geochemistry Department of Exploration and
Production in 1982. After 7 years in research, Peter worked as
geochemical advisor in Canada, Oman and the United States, before
returning to Shell International in early 2005. In the last three
years, Peter has worked on projects in support of E&P ventures in
North Africa and the Middle East.

Peter served on the board of the European Association of Organic

Geochemists from 1991 to 1998 and was a member of the first
editorial board of GeoArabia when it was launched in 1995. Peter and
co-authors have received best paper awards from both the AAPG and
SPWLA for their work on the Athel Formation in Oman

Dr. Peter Nederlof is currently the Lecturer for EAGEs Student

Lecture Tour for the Middle East 2008 and will be covering the New

Applications in Petroleum Geochemistry.

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

Part II Introduction to Petroleum Geochemistry

- Thermal Cracking of Source Rocks, Oil Typing and
Oil-to-Source Rock Correlation
Part III New Applications
- Operational Geochemistry, Dry Hole Analysis,
Unconventional Resources

Carbon

4th most abundant chemical element in the universe (after H, He and O)

unique property to bond with itself and form millions of hydrocarbon molecules
occurs in all organic life and is the basis for organic chemistry
molecular weight of 12 (6 protons, 6 neutrons, 6 electrons)

 unique property to bond with itself

and form millions of hydrocarbon molecules
Gases: one to four carbon atoms
H
H

Methane
CH4

Ethane
CH3CH3

H
H

CH 2

CH 2

CH 2

CH 2

Hexane
C6H12

H
H

n-Butane

Propane
CH3CH2CH3

Liquids: Five to 40+ carbon atoms

CH 3

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 =

Carbon isotope abundances are expressed as

the ratio of 13C to 12C isotopes in the sample
compared to the same ratio in a standard.
Because the differences in ratios are very small,
they are expressed as parts per thousand or 'per
mil' () deviation from the standard

(13C/12C sample) - (13C/12C standard)

(13C/12C standard)

x 1000

The standard is defined as 0. The international standard is Pee Dee Belemnite,

a fossil collected from the banks of the Pee Dee River in South Carolina with a
13C/12C ratio of 0.0112372.
Carbon compounds with ratios of 13C/12C > 0.00112372 have positive delta values, and those
with ratios of 13C/12C < 0.00112372 have negative delta values.

Isotopic composition of crude oils reflects their source rock

Isotopically Light
-36

-34

-32

-30

Isotopically Heavy
-28

-26

-24

-22

-20
Tertiary
Kalash Fm.
Sirt Fm.
Rachmat Fm

Source Rock from the Sirte

Basin in Libya have different
carbon isotope ratios.
Oil can often be attributed to
source rock on the basis of
carbon isotope ratios

Etel Fm.
Cretaceous/Nubian
Triassic

Silurian Shales

Carbon Cycle: Definition

The global scale exchange of carbon among its
reservoirs, namely the atmosphere, oceans,
vegetation, soils, and geologic deposits and
minerals.
www.climatechange.ca.gov

Carbon Cycle Schematic Diagram

www.physicalgeography.net

Carbon Cycle and Sediment

Carbon Sink
Sink
Photosynthesis

CO2
Atmosphere

C
Plant Life
Degradation
Respiration

99.9 %

0.1 %

Sediment
Sink

After John M. Hunt, Petroleum Geochemistry and Geology (1995)

Cum. area of SR (000 km2)

Deposition of Carbon over Geologic Time

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

Carbon Cycle: the Sediment Sink

Photosynthesis

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

Atmospheric CO2 (ppm) as a function of time (Ma)

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)

Question: how did it get there?

Source Rock
Evaluation
(Petroleum Geochemistry)

Petroleum Geochemistry is the application of

chemical principles to the study of the
origin, migration, accumulation and alteration of oil and gas
and the use of this knowledge in exploring for and recovering petroleum
John M. Hunt,
Petroleum Geochemistry and Geology
W.H. Freeman and Company (1996)

12

What does a petroleum geochemist do all day?

1. Try to understand the filling history of oil accumulations
2. Build models that explains oil fields in terms of
(1) presence and maturity of source rock,
(2) migration history
(3) retention and alteration
3. Use the model to predict where more oil can be found and to
optimize oil recovery from the field

Egypt: Abu Gharadig Basin - Stratigraphy

Abu Roash Source Rock

40% of oil reserves

60% of oil reserves

13

What is a source rock?

A rock which contains sufficient organic matter to generate commercial
quantities of hydrocarbons
upon reaching thermal maturity

Hydrocarbons have a biological origin

Oils and gases can be linked to specific source rocks by the

presence of certain components and their isotopic signature.

Chemical compounds within the source rock and produced

hydrocarbons can be linked to molecules within living plants

14

Primary Sources of Organic Carbon in Sediments

Phytoplankton
Zooplankton
Algae, bacteria etc.
Land plants

> 99%

< 1%

Anything else that has ever lived

Cairo Daily News July 30, 2008

Photosynthesis

Source Rock Deposition:

Productivity and Preservation
CO2
Atmosphere

Carbon Cycle
0.02 %

Degradation
Respiration

Torbanite Algal Coal, Scotland

C
Plant life

Sediment
Sink

Silurian hot shale, Middle East

15

Areas of high primary productivity in the present day oceans

Primary productivity is only one control on source rock deposition

Primary Productivity

Sunlight
Carbon Dioxide - Oxygen
Nutrients; N, P, Si, Fe, Ni, V, Zn, Cu

January

July

Zooplankton

Phytoplankton

Nutrients
Sunlight

Primary Productivity in Northern Hemisphere Inshore Waters

December

16

Algal blooms off the coast of Florida as a result of African dust

NASA/Goddard Space Flight Center

Ceratium hirundinella,
(Dinoflagellate)

Preservation: bottom water euxinic conditions

Bosphorus
Sea of
Marmora

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

Preservation: Pro-deltaic Shales

Water column stratification

Bottom water anoxia
River River
input Input
Swamps

Lakes

stratification
Flux of terrigenous
and marine OM

Low oxygen

Pro-deltaic shales

Preservation: Carbonate Platforms

Restricted Bottom water circulation

Low sedimentation rate

Thermally stratified water column

Restricted bottom
water circulation

Area of high productivity

Carbonate build-ups
Intra-basinal sags

18

Preservation: Upwelling

Water column stratification

Oxygen minimum zone

Offshore winds
Area of high productivity

OMZ

N P Si

Cold nutricient rich waters

Cum. area of SR (000 km2)

Source rocks are not distributed equally in time

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

The Greenhouse World

shelf anoxia

Small difference in temperature between poles

and equator
Expanded tropical and temperate climate belts
Sluggish oceanic circulation
Upwelling decreases
Oxygen poor bottom waters
Sea level rises - anoxic shelves common

high productivity
strongly stratified water column

OMZ

sluggish bottom water circulation

example: Expanded Oxygen Minimum Zones

The Icehouse World

Large difference in temperature between poles
and equator
Compressed tropical and temperate climate
belts
Intense oceanic circulation
Upwelling increases
Oxygen rich bottom waters
Sea level drops - restricted basins common

Polar Region

less dense warm surface waters

ice
dense oxygen rich btm water

example: Oxygen Rich Bottom Waters

Source Rock Deposition: Productivity and Preservation

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

Source Rock Analysis

TOC wt%

15,000

S2 mgHC/g rock

16,000

17,000

There is more to source rock

analysis than measuring TOC ...

18,000

19,000

20,000

21,000

22,000

TOC log for a well in the

Gulf of Mexico

23,000

24,000
0

10

11

12

13

14

15

A complete source rock evaluation consists of:

TOC measurement

..

Richness

Rock Eval Analysis

..

Type and Maturity

Visual Kerogen Analysis

..

Contamination, Type, Maturity

Solvent Extraction

..

Type, Maturity

Petrophysical Log Evaluation .

Thickness

SPI calculation

..

Charge volume estimate

Source Rock Kinetics

..

Conversion as a function of maturity

Compositional kinetics

..

Product Mix as a function of Maturity

.. 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

Total Organic Carbon (TOC): What makes a good source rock?

TOC in Shales (%)

TOC in Carbonates (%)

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

Source Rock Pyrolysis

Rock-Eval, PFID
Rock Eval Analysis

temperature

Generation Potential

Tmax
Trapping
of CO2

S1 : already generated HC + base oil

contamination

time

S2 : remaining generative potential

(mg HC/g rock)

S2 : is a good measure for source rock

quality (at low maturities)
S2 > 5 mgHC/g rock is good SR

S1

Thermal
extraction

S2

Pyrolysis

S3

CO2 release

22

Source Rock Evaluation Syria

TOC, Rock Eval S2 vs. Depth

1800

2000

2000

2200

2200

2400

2400

2600

2600

Depth (m)

Depth (m)

1800

2800

2800

3000

3000

3200

3200

3400

Rock Eval Tmax vs. Depth

3400

Rock Eval S2
TOC

3600

3600

3800

3800
0

10

15

TOC (% wt)

20

25

426 428 430

432 434 436 438 440 442

444 446 448

Tmax (C)

Hydrogen Index (HI):

100 * S2/TOC
Oxygen Index (OI):
100 * S3/TOC
Tmax:
Temperature at which S2
peaks (measure of maturity)

23

TOC and Rock Eval S2 vs. Depth

2200

Source Rock Screening

in Syria

TOC vs. Rock Eval S2

2600

40

R ock Eval S2

Rock Eval S2 (mg HC)

Depth (m)

2400

TOC
2800

3000
0

10

15

TOC (%wt)

20

25

30

HI = 770

20

10

0
0

TOC

Kerogen Type and Molecular Composition

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

Kerogen Structures according to Behar et al.

Type I

Type II

Type III

Qusaiba Rock Eval Data Saudi Arabia

after Cole et al. Energy and Fuel (1994) pp 1425 - 1442

HI of 300

25

Visual Kerogen Analysis (VKA)

Microscopy with tungsten & UV light of polished whole rock samples

SR quality (maceral composition)

SR type (oil vs. gas)
Expulsion capacity
Environment of deposition
Maturity (Vitrinite Reflectance)

Visual Kerogen Analysis

Silurian, Syria
Good, post mature, Type II source rock (TOC-1.6%).
Photomicrograph, showing lenses of SOM associated with framboidal pyrite.

26

Every source rock evaluation should

address
both quality and quantity

The SPI is a good measure of the

source potential of a basin

SPI = the mass of HC in metric tons

that is generated at full maturity from
a column of rock below 1 m2.

Influence of Drainage Area Size

Classification of low or high SPI

depends on the size of the drainage area
and hence on whether lateral or vertical
migration is dominant

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

Part II Introduction to Petroleum Geochemistry

- Thermal Cracking of Source Rocks, Oil Characterisation,
Oil-to-Source Rock Correlation
Part III New Applications
- Operational Geochemistry, Dry Hole Analysis,
Unconventional Resources

29

Hydrocarbon Generation and Expulsion

Source Rock Kinetics
The conversion of a source rock into oil and gas is governed by:
Source rock thermal history:
10% input uncertainty results in 10 - 40% output uncertainty
Chemical kinetics of kerogen conversion:
10% input uncertainty results in 20 - 50% output uncertainty
Kerogen conversion is a linear function of time and an exponential function of
temperature. We model the conversion of kerogen to petroleum as a series of parallel
first order reactions governed by the Arrhenius rate law.

Kerogen:
Kinetics:

the organic matter contained in source rocks

a branch of chemistry which studies the relationship between rate of a reaction, the temperature
and the concentration of the reagents

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)

Xi = Concentration of kerogen component i

Ki = Rate constant (per sec) for reaction i
Ai = Frequency Factor (per sec) for reaction i
Ei = Activation Energy (KCal/mol) for reaction i
t = time (sec)
T = Temperature

30

1. Discrete Distribution of Ea

Kerogen Kinetics (1)

0.3

Ea (kcal/mol)

0.2

The frequency factor (A) and activation

energy (Ea) describe the kerogen
response to temperature. Because
kerogen is a complex mixtures of
components with different kinetic
properties, there is a distribution of
activation energies.

67

63

55

51

59

0.1

2. Gaussian about Ea Mean, a

Basin models commonly represent this

distribution in one of three ways.

Ea mean
3. Single start and end Ea

The distribution of Ea can be

determined by laboratory
measurements

Ea start

Ea end

Kerogen Kinetics (2)

For a simple temperature history, a spreadsheet calculation produces curves of
predicted source rock conversion vs. temperature.

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)

120 140 160 180

200 220
o
Temp ( C)

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

In Situ Conversion Process

Mahogany Research Project

Rio Blanco County, Colorado
1400 bbl/d

32

Source Rock Burial History

90 C

150 C

Basin Modeling

Please remember: the model is

only as good as its input material

33

Conclusions (Part II)

-Oil and gas are formed through the thermal cracking of kerogen, a process
that can be simulated in the lab and modeled accurately

Next question:
Where does the generated oil go?

Tar Lake in Trinidad

34

Oil Analysis:
Gas Chromatography

Oils can be separated into individual

components by gas chromatography
Some columns separate on boiling point,
(molecular size), others on polarity.

Whole Oil Gas Chromatography: Source

Marine SR
North Sea

Algal SR
Thailand

Carbonate SR
Oman

Landplant SR
Far East

35

Whole Oil Gas Chromatography: Maturity

Whole Oil Gas Chromatography: Biodegradation

6,836 ftft
10,000

9,262ftft
8,120

9,262ft ft
8,120
9,262 ft

10,000 ft
6,836 ft

36

Molecular Fossils

Cholesterol

Cholestane

Oil Typing: Molecular Fossils

ant
bund
a
t
s
o
he m
earth
are t icals on
s
d
i
em
ano
Hop tural ch
na

37

Molecular Fossils are used for

oil/source correlations

Egypt: Abu Gharadig Basin - Stratigraphy

Abu Roash Source Rock

Question:
Is there more than one oil source
rock in the Abu Gharadig Basin,
Egypt ?

38

Abu Gharadig Basin Charge Concept

Safa

Khoman B

Bahariy
a
Kharita
Alamein
Alam El Bueib
Masajid
Khatatba

Abu Gharadig Basin Seismic Section

BED 4-1

Source Rock

39

Badr El Din 4-1

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

Highly mature Khatatba oil

-25.0
-26.0

BED 4-1
Kharita 3696m

-27.0

BED 4-1 Abu

Roash 2946m

-28.0

C17

Low mature Abu Roash oil

-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

Molecular Fossils: Sterane Distributions

C27

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

Molecular Fossils: Triterpane Distributions

C30
BED 4-1
Abu Roash-F oil
2946 m

C29

24/4

Tm
Ts

C30

BED 4-1
Kharita oil
3636 m

C29
Tm
24/4

Diahopane

Ts

Egypt: Abu Gharadig Basin - Stratigraphy

Abu Roash Source Rock

Answer:
There are 2, may-be even 3 source
rocks in the Jurassic Khatatba Fm.

Khatatba Source Rocks

41

Conclusions (Part II)

- 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

Part II Introduction to Petroleum Geochemistry

- Thermal Cracking of Source Rocks, Oil Characterisation,
Oil-to-Source Rock Correlation
Part III New Applications
- Operational Geochemistry, Dry Hole Analysis,
Unconventional Resources

43

New Directions in Petroleum Geochemistry

1.

Analytical equipment is moving to the well-site: real-time operational geochemistry

2.

More powerful analytical instrumentation: dry hole analysis

3.

Unconventional resources: different analytical programs

1. Operational
Geochemistry
Mud Gas Logging

Mud Circulation System:

1.
2.
3.

to cool the drill bit

to control the pressure
to remove drill cuttings and gas
released during drilling

44

Logging
While
Drilling

Mud Gas Logging: Gas Extraction

45

Advanced Mud Logging: Reserval and Flex Flair (1)

1. Qualitative Gas Extraction
Constant Volume Gas Extractor
Analysis by Gas Chromatography
(Geoservices Reserval)
3. Mudgas sampling program for
carbon isotope analysis

Intake Probe

2. Quantitative Gas Extraction

Constant PVT conditions
Correction for gas in
Analysis by Mass Spectrometry
(Geoservices Flex Flair)

Advanced Mud Logging: Reserval and Flex Flair (2)

Sampling configuration at Seraj well
Probe in flow line

Fluid Extractor - out

46

Advanced Mud Logging: Reserval and Flex Flair (3)

Data transmission system:

Real time lithology, MWD,
Mud gas compositions from
any PC with internet access

Advanced Mud Logging: Reserval and Flex Flair (4)

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

Continuous Fluid Logging in the Gulf of Mexico

Yellow Reservoir Prospect P.
23000

GOR predicted from Flex Flair

23050
23100
23150
23200
23250
23300
23350
23400
23450
23500
0

3000

6000

9000

12000

15000

Accuracy: Example from GoM well O.

48

Methane Carbon Isotope vs. Depth

-75.0

-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

Methane Carbon Isotope vs. Depth

-75.0
75.0

-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

Methane Carbon Isotope vs. Depth

-75.0

-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

Prospect S (GoM): dry hole

Any evidence of charge? Up-dip potential? Sidetrack? PA/TA?

A
B
C

50

Prospect S (GoM): dry hole

Any evidence of charge? Up-dip potential? Sidetrack? PA/TA?

Fluid Inclusion Screening

Present-day formation fluids,
trapped/adsorbed in the sediments.
May not be actual fluid inclusions
Trapped fluids liberated by mechanical
crushing
Released volatiles analysed by mass
spectrometry
Migration pathways: Methane, Ethane,
Paraffin, C-3 plus Naphthene
Proximity to Pay: Methane, H2S, CO2,
Benzene, Toluene, Acetic Acid

51

Fluid Inclusion Screening: Proximity to Pay indicators (PTP)

Conclusions (Part III)

- There is new high-tech mud logging technology, which allows the evaluation of
hydrocarbon charge systems, provide information on migration style, and can
sense nearby oil accumulations

52

2. Dry Hole Analysis

Looking for evidence of
hydrocarbons in dry holes

D2-NC41
B3-NC41 B1-NC41
E1-NC41
D1-137
C1-137
C1-NC41

Geochemical Well Evaluations

Offshore Libya

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

xploration & Production Libya GmbH

nformation:
979_UTM_Zone_34N
ion: Transverse_Mercator
Easting: 500000.0
Northing: 0.0
_Meridian: 21.0
Factor: 0.9996
e_Of_Origin: 0.0

53

Potential Source Rocks

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

xploration & Production Libya GmbH

nformation:
979_UTM_Zone_34N
ion: Transverse_Mercator
Easting: 500000.0
Northing: 0.0
_Meridian: 21.0
Factor: 0.9996
e_Of_Origin: 0.0

54

Fluid Inclusion Screening

Output from FIT, Tulsa

Methane: CH3+ (m/e 15)

Ethane: C2H5+ (m/e 29)
Benzene:C6H5+ (m/e 78)
Cycloalkanes: C7H13+ (m/e 97)

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

Extract Analysis (9,270 9,580 ft)

-23.0

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

Compound Specific Isotope Analysis (CSIA)

Micro-show analysis

1 gram
C1

C2

C3

iC4

nC4

iC5

nC5

-15.0
-20.0
-25.0
-30.0
-35.0
-40.0
-45.0

gases of Silurian origin

-50.0
-55.0
-60.0

evidence for presence of micro-shows

good match with Silurian sourced gases

56

Compound Specific Isotope Analysis (CSIA)

C1

C2

C3

iC4

nC4

iC5

nC5

-20
-25
-30
-35
-40
-45
-50
-55

Compound Specific Isotope Analysis (CSIA)

57

Conclusions (Part III)

-There is new high-tech mud logging technology, which allows the evaluation of
hydrocarbon charge systems, provide information on migration style and can
sense nearby oil accumulations
- Developments in analytical chemistry have made it possible to identify microshows in cuttings from wells that were drilled many years ago.

3. Unconventional
Resources
Shale Gas

58

Conventional Oil and Gas discovered per year 1918-2006

Discovered Recoverable (Gboe) per year
Binned by 3 Years periods and Volume classes
21430 Datapoints

120
> 500 MMBoe

Discoverd Recoverable Volumes (Gboe/Year)

400 . 500 MMBoe

100

300 . 400 MMBoe

200 . 300 MMBoe
100 . 200 MMBoe
0 . 100 MMBoe

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

Discovery Year Periods

The Energy World is Changing

1. Global energy demand is accelerating
- Energy essential for economic growth and social development
- Developing economies enter energy intensive phase
- XOM: +30% by 2020, RDS: +100% 2050
2. Conventional resources will struggle to keep up with demand
- HCs provide 80% of global energy supply
- Renewables will play increasing role, but will be unable to meet demand
- Shift towards unconventionals: shale gas, heavy oil, tar sands
3. Increased coal use will cause higher CO2 emissions, possibly to levels we
deem unacceptable
- share of coal is set to grow (widespread geographic availability)
- unless steps are taken to manage CO2 , emissions will continue to increase

59

Petroleum Systems Inefficiencies

Expulsion
losses

Seepage to
surface

Migration
losses

Sub-economic
traps

Amount
generated
Amount trapped

Fractured Shale Play, Continental US

60

Gas Production from Fractured Shales is not new

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

Fractured Barnett Shale Gas (Ft Worth Basin, Texas)

27 TCF Natural Gas Resource

wet

62

Barnett Production Sweet Spot

eerraattiioonn
n
e
n
G
e
.
11. G
ntiioonn
22.. RReetteent ibiilliittyy
uc ib
33.. PPrroodduc

Source Rock Conversion vs. Maturity

Conversion

For Type I, II and III Kerogens

1.0
0.8
0.6
0.4
0.2
0

0.4

0.6

1.2

2.0

Maturity (VRE)

63

Shale Gas Evaluation Criteria (Jarvie)

Unconventional Resources: Phase Behaviour

Production of an adsorbed gas from a surface area
follows different physical laws that production of
gas from the pore space.

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

Gas adsorption on shales

adsorbate

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

Sorption Capacity (scf/ton)

100

80

60

40
T =145 F
T =175 F

20

0
0

1000

2000

3000

4000

Pressure (psi)

65

Langmuir Adsorption Isotherm

= 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)

Gas forms a film on the solid substrate

Barnett vs. Antrim Langmuir Isotherms

B arnett S hale (TOC =4.00wt% )

Sorption Capacity (scf/ton)

80

A ntrim S hale (TOC =7.8wt% )

60

40

20

0
0

1000

2000

3000

4000

R eservoir Pressu re (ps ia)

66

Are there any other selection criteria?

Burial History of Barnett Shale in Wise County, Texas

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

Conclusions (Part III)

-There is new high-tech mud logging technology, which allows the evaluation of
hydrocarbon charge systems, provide information on migration style and can
sense nearby oil accumulations
-Developments in analytical chemistry have made it possible to identify microshows in cuttings from wells that were drilled many years ago.
-Development of Unconventional Resources will require entirely new tools and
new capabilities and unconventional screening methods

68

Acknowledgments
Andy Bell (Shell)
Johan Buiskool Toxopeus (Shell)
Andrew Murray (Woodside)
Shannon de Groot (EAGE)

Thank you for your attention

Questions, Comments?
p.nederlof@shell.com

69

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